WO2022029884A1 - Gas production apparatus, gas production system, and gas production method - Google Patents

Gas production apparatus, gas production system, and gas production method Download PDF

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Publication number
WO2022029884A1
WO2022029884A1 PCT/JP2020/029820 JP2020029820W WO2022029884A1 WO 2022029884 A1 WO2022029884 A1 WO 2022029884A1 JP 2020029820 W JP2020029820 W JP 2020029820W WO 2022029884 A1 WO2022029884 A1 WO 2022029884A1
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Prior art keywords
gas
raw material
reducing
reducing agent
carbon dioxide
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PCT/JP2020/029820
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French (fr)
Japanese (ja)
Inventor
友樹 中間
アルツゲ ラシカ ダサナヤケ
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to PCT/JP2020/029820 priority Critical patent/WO2022029884A1/en
Priority to JP2022541373A priority patent/JPWO2022029884A1/ja
Priority to EP20948667.9A priority patent/EP4194399A1/en
Priority to US18/019,561 priority patent/US20230365414A1/en
Publication of WO2022029884A1 publication Critical patent/WO2022029884A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132—Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/06—Details of tube reactors containing solid particles
    • B01J2208/065—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/008—Feed or outlet control devices

Definitions

  • the present invention relates to a gas production apparatus, a gas production system, and a gas production method.
  • Patent Document 1 discloses a technique for converting carbon dioxide into a valuable substance. Specifically, a manufacturing apparatus for producing carbon monoxide from carbon dioxide using cerium oxide containing zirconium is disclosed.
  • Patent Document 1 is an invention for specifying a metal oxide that effectively converts carbon monoxide from carbon dioxide.
  • Patent Document 1 only discloses conceptual or general information as shown in the drawings in terms of carbon monoxide production conditions and production equipment, and industrially produces carbon monoxide. It turned out that further technical improvement was necessary for this. Therefore, an object of the present invention is a gas production apparatus (that is, an industrially advantageous production apparatus) capable of continuously and stably producing a produced gas containing carbon monoxide from a raw material gas containing carbon dioxide. To provide a gas production system and a gas production method.
  • the gas production apparatus of the present invention is a gas production device that produces a produced gas containing carbon monoxide by contacting a raw material gas containing carbon dioxide with a reducing agent containing the metal oxide that reduces carbon dioxide. It ’s a device, The raw material gas supply unit that supplies the raw material gas and A reducing gas supply unit that supplies a reducing gas containing a reducing substance that reduces the reducing agent oxidized by contact with carbon dioxide, and a reducing gas supply unit. A plurality of reactors connected to the raw material gas supply unit and the reducing gas supply unit, and the reducing agent arranged in the reactor are provided, and the raw material gas and the reduction are supplied to each of the reactors. It has a reaction unit that can switch between gas and gas.
  • the raw material gas supplied to each of the reactors is used. It is characterized in that it is configured to switch with the reducing gas.
  • the supply amount of the raw material gas to the reactor is P [mL / min], and the supply amount of the reducing gas to the reactor is Q [mL / min]. When this is done, it is preferable to satisfy the relationship in which P / Q is 0.9 to 2.
  • the predetermined amount may be 0.01 to 3 mol of carbon dioxide per 1 mol of the metal element having the largest mass ratio in the reducing agent. preferable.
  • the predetermined value is preferably 50 to 100%.
  • the gas production apparatus of the present invention further has a heat exchanger that exchanges heat between the mixed gas and the raw material gas before being supplied to the reactor.
  • the metal oxide preferably contains at least one selected from the metal elements belonging to Group 3 to Group 12.
  • the gas production system of the present invention is A raw material gas generator that generates raw material gas containing carbon dioxide, Equipped with the gas production apparatus of the present invention The gas production apparatus is connected to the raw material gas generation unit via the raw material gas supply unit.
  • a raw material gas containing carbon dioxide is brought into contact with a reducing agent containing a metal oxide that reduces carbon dioxide to produce a gas containing carbon monoxide.
  • a reducing agent containing a metal oxide that reduces carbon dioxide to produce a gas containing carbon monoxide.
  • a plurality of reactors in which the reducing agent is arranged, a reducing gas containing the raw material gas and a reducing substance that reduces the reducing agent oxidized by contact with the carbon dioxide are prepared.
  • the raw material gas and the reducing gas are alternately brought into contact with the reducing agent in each of the reactors, and the carbon dioxide is brought into the one. After converting to carbon oxide, the oxidized reducing agent is reduced to reduce it.
  • the gases after passing through the reactor are merged to generate a mixed gas.
  • the mixed gas As it is or by purifying the carbon monoxide from the mixed gas as the produced gas.
  • the raw material gas supplied to each of the reactors is used. It is characterized by switching from the reducing gas.
  • a produced gas containing carbon monoxide can be efficiently and continuously produced from a raw material gas containing carbon dioxide.
  • the above effect can be further improved by adjusting the switching timing between the raw material gas supplied to the reactor and the reducing gas.
  • FIG. 1 is a schematic view showing an embodiment of the gas production system of the present invention
  • FIG. 2 is a cross-sectional view schematically showing the configuration of the reactor of FIG. 1
  • FIG. 3 is an exhaust gas of FIG. It is a schematic diagram which shows the structure of the heating part.
  • the gas production system 100 shown in FIG. 1 comprises a furnace (raw material gas generation unit) 20 that generates exhaust gas (raw material gas) containing carbon dioxide, and a gas production apparatus 1 connected to the furnace 20 via a connection unit 2.
  • the upstream side with respect to the gas flow direction is also simply referred to as “upstream side”, and the downstream side is simply referred to as “downstream side”.
  • the furnace 20 is not particularly limited, but is, for example, a furnace attached to a steel mill, a smelter, or a thermal power plant, and preferably includes a combustion furnace, a blast furnace, a converter, and the like.
  • exhaust gas is generated (generated) when the contents are burned, melted, refined, or the like.
  • the contents include, for example, plastic waste, swill, urban waste (MSW), waste tires, biomass waste, and household waste (futon). , Paper), building materials, etc.
  • these wastes may contain 1 type alone or 2 or more types.
  • Exhaust gas usually contains carbon dioxide as well as other gas components such as nitrogen, oxygen, carbon monoxide, water vapor and methane.
  • concentration of carbon dioxide contained in the exhaust gas is not particularly limited, but is preferably 1% by volume or more, more preferably 5% by volume or more, in consideration of the production cost of the produced gas (efficiency of conversion to carbon monoxide).
  • carbon dioxide is contained in an amount of 5 to 15% by volume
  • nitrogen is contained in an amount of 60 to 70% by volume
  • oxygen is contained in an amount of 5 to 10% by volume
  • water vapor is contained in an amount of 15 to 25% by volume.
  • the exhaust gas from the blast furnace (blast furnace gas) is a gas generated when pig iron is produced in the blast furnace, and carbon dioxide is 10 to 15% by volume, nitrogen is 55 to 60% by volume, and carbon monoxide is 25 to 30% by volume.
  • Hydrogen is contained in 1-5% by volume.
  • the exhaust gas (converter gas) from the converter is a gas generated when steel is manufactured in the converter, and carbon dioxide is 15 to 20% by volume, carbon monoxide is 50 to 60% by volume, and nitrogen is. It contains 15 to 25% by volume and 1 to 5% by volume of hydrogen.
  • the raw material gas is not limited to the exhaust gas, and a pure gas containing 100% by volume of carbon dioxide may be used.
  • exhaust gas is used as the raw material gas, carbon dioxide conventionally emitted into the atmosphere can be effectively used, and the burden on the environment can be reduced.
  • exhaust gas containing carbon dioxide generated in a steel mill or a refinery is preferable.
  • the blast furnace gas or the linz-donaw gas the untreated gas discharged from the furnace may be used as it is, or for example, the treated gas after being treated to remove carbon monoxide or the like may be used. good.
  • the untreated blast furnace gas and the linz-Donaw gas each have a gas composition as described above, and the treated gas has a gas composition close to the gas composition shown in the exhaust gas from the combustion furnace.
  • any of the above gases gas before being supplied to the gas production apparatus 1 is referred to as exhaust gas.
  • the gas production apparatus 1 includes an exhaust gas (raw material gas containing carbon dioxide) discharged from the furnace 20 and supplied via the connection portion 2, and a reducing agent containing a metal oxide that reduces carbon dioxide contained in the exhaust gas. To produce a produced gas (synthetic gas) containing carbon monoxide.
  • the gas production apparatus 1 mainly includes a connection unit 2, a reducing gas supply unit 3, two reactors 4a and 4b, a gas line GL1 connecting the connection unit 2 and the reactors 4a and 4b, and reduction. It has a gas line GL2 connecting the gas supply unit 3 and the reactors 4a and 4b, and a gas line GL4 connected to the reactors 4a and 4b.
  • connection unit 2 constitutes a raw material gas supply unit that supplies exhaust gas to the reactors 4a and 4b.
  • a pump for transferring gas may be arranged at a predetermined position in the middle of the gas line GL1, the gas line GL2, and the gas line GL4. For example, when the pressure of the exhaust gas is adjusted to be relatively low by the compression unit 6 described later, the gas can be smoothly transferred in the gas production apparatus 1 by arranging the pump.
  • the gas line GL1 is connected to the connecting portion 2 at one end thereof.
  • the gas line GL1 is connected to the inlet ports of the reactors 4a and 4b provided in the reaction unit 4 via the gas switching unit 8 and the two gas lines GL3a and GL3b at the other end.
  • the gas switching unit 8 can be configured to include, for example, a branched gas line and a flow path opening / closing mechanism such as a valve provided in the middle of the branched gas line.
  • each reactor 4a and 4b is a multi-tube reactor (fixed) including a plurality of tubular bodies 41 each filled with a reducing agent 4R and a housing 42 containing the plurality of tubular bodies 41. It is composed of a layered reactor). According to such a multi-tube reactor, it is possible to sufficiently secure an opportunity for contact between the reducing agent 4R and the exhaust gas and the reducing gas. As a result, the production efficiency of the produced gas can be improved.
  • the reducing agent 4R of the present embodiment is preferably in the form of particles (granule), scales, pellets, or the like.
  • the filling efficiency into the tube 41 can be increased, and the contact area with the gas supplied into the tube 41 can be further increased.
  • its volume average particle size is not particularly limited, but is preferably 1 to 50 mm, more preferably 3 to 30 mm.
  • the contact area between the reducing agent 4R and the exhaust gas (carbon dioxide) can be further increased, and the conversion efficiency of carbon dioxide into carbon monoxide can be further improved.
  • the regeneration (reduction) of the reducing agent 4R with a reducing gas containing a reducing substance can be performed more efficiently. Since the particulate reducing agent 4R has a higher sphericity, it is preferably a molded product produced by rolling granulation.
  • the reducing agent 4R may be supported on a carrier.
  • the constituent material of the carrier may be any material that is not easily modified depending on the exhaust gas (raw material gas), reaction conditions, etc., and is not particularly limited.
  • carbon material graphene, graphene, etc.
  • zeolite zeolite
  • montmorillonite SiO 2 , ZrO 2 , TiO 2 , V 2 O 5 , MgO, alumina (Al 2 O 3 ), silica, and composite oxides of these materials.
  • zeolite, montmorillonite, SiO 2 , ZrO 2 , TiO 2 , V 2 O 5 , MgO, alumina (Al 2 O 3 ), silica, and composite oxides of these materials are preferable.
  • a carrier composed of such a material is preferable in that it does not adversely affect the reaction of the reducing agent 4R and is excellent in the carrying capacity of the reducing agent 4R.
  • the carrier does not participate in the reaction of the reducing agent 4R, but merely supports (retains) the reducing agent 4R.
  • the metal oxide (oxygen carrier) contained in the reducing agent 4R is not particularly limited as long as it can reduce manganese, but contains at least one selected from the metal elements belonging to Group 3 to Group 12. It is preferable, and it is more preferable to contain at least one selected from the metal elements belonging to the 4th to 12th genera, among titanium, vanadium, iron, copper, zinc, nickel, manganese, chromium, cerium and the like. It is more preferable to contain at least one of the above, and a metal oxide or a composite oxide containing iron is particularly preferable. These metal oxides are useful because they have particularly good conversion efficiency of carbon dioxide to carbon monoxide.
  • the tubular body (cylindrical molded body) 41 may be produced by the reducing agent 4R (metal oxide) itself.
  • a block-shaped, lattice-shaped (for example, net-shaped, honeycomb-shaped) molded body may be produced with the reducing agent 4R and arranged in the housing 42.
  • the reducing agent 4R as a filler may be omitted or may be used in combination.
  • a configuration in which a network body is produced with the reducing agent 4R and arranged in the housing 42 is preferable.
  • the volumes of the two reactors 4a and 4b are set to be substantially equal to each other, and are appropriately set according to the amount of exhaust gas to be treated (the size of the furnace 20 and the size of the gas production apparatus 1).
  • a concentration adjusting unit 5 adjusts so as to increase the concentration of carbon dioxide contained in the exhaust gas (in other words, to concentrate carbon dioxide).
  • Exhaust gas also contains unnecessary gas components such as oxygen.
  • the concentration adjusting unit 5 is preferably configured by an oxygen removing device that removes oxygen contained in the exhaust gas.
  • an oxygen removing device that removes oxygen contained in the exhaust gas.
  • the amount of oxygen brought into the gas production apparatus 1 can be reduced (that is, the concentration of oxygen contained in the exhaust gas can be adjusted to be low). Therefore, the gas composition of the exhaust gas can be deviated from the explosion range, and the ignition of the exhaust gas can be prevented. It should be noted that, among the gas production apparatus 1, since the oxygen removing apparatus consumes a large amount of electric energy, it is effective to use electric power as renewable energy as described later.
  • the concentration of oxygen contained in the exhaust gas is preferably adjusted to less than 1% by volume, more preferably less than 0.5% by volume, and less than 0.1% by volume with respect to the entire exhaust gas. It is more preferable to adjust. This makes it possible to more reliably prevent the ignition of the exhaust gas.
  • Oxygen removal devices that remove oxygen contained in exhaust gas include low temperature separation type (deep cooling type) separators, pressure swing adsorption (PSA) type separators, membrane separation type separators, and temperature swing adsorption (TSA). It can be configured by using one or more of a type separator, a chemical absorption type separator, a chemical adsorption type separator and the like.
  • the concentration adjusting unit 5 may adjust the concentration of carbon dioxide to a high concentration by adding carbon dioxide to the exhaust gas.
  • the compression unit 6 raises the pressure of the exhaust gas before supplying it to the reactors 4a and 4b. This makes it possible to increase the amount of exhaust gas that can be processed at one time by the reactors 4a and 4b. Therefore, the conversion efficiency of carbon dioxide into carbon monoxide in the reactors 4a and 4b can be further improved.
  • the compression unit 6 includes, for example, a centrifugal compressor, a turbo compressor such as an axial flow compressor, a reciprocating compressor (recipro compressor), a diaphragm compressor, a single screw compressor, a twin screw compressor, and the like.
  • It can be composed of a scroll compressor, a rotary compressor, a rotary piston type compressor, a positive displacement compressor such as a slide vane type compressor, a roots blower (two-leaf blower) capable of supporting low pressure, a centrifugal blower, and the like.
  • the compression unit 6 is preferably configured by a centrifugal compressor from the viewpoint of easiness of increasing the scale of the gas production system 100, and from the viewpoint of reducing the production cost of the gas production system 100, it is preferable. It is preferable to use a reciprocating compressor.
  • the pressure of the exhaust gas after passing through the compression unit 6 is not particularly limited, but is preferably 0 to 1 MPaG, more preferably 0 to 0.5 MPaG, and preferably 0.01 to 0.5 MPaG. More preferred. In this case, the conversion efficiency of carbon dioxide into carbon monoxide in the reactors 4a and 4b can be further improved without increasing the pressure resistance of the gas production apparatus 1 more than necessary.
  • the fine component removing unit 7 removes fine components (trace amount of unnecessary gas components, etc.) contained in the exhaust gas.
  • the fine component removing unit 7 can be composed of, for example, a processor of at least one of a gas-liquid separator, a protector (guard reactor), and a scrubber (absorption tower).
  • the order of arrangement thereof is arbitrary, but when using the gas-liquid separator and the protector in combination, it is preferable to arrange the gas-liquid separator on the upstream side of the protector. .. In this case, the efficiency of removing fine components from the exhaust gas can be further improved, and the usage period (life) of the protector can be extended.
  • the gas-liquid separator separates, for example, the condensed water (liquid) generated when the exhaust gas is compressed by the compression unit 6 from the exhaust gas. In this case, unnecessary gas components remaining in the exhaust gas are also dissolved and removed in the condensed water.
  • the gas-liquid separator can be composed of, for example, a simple container, a swirling flow separator, a centrifuge, a surface tension separator, or the like. Among these, the gas-liquid separator is preferably composed of a simple container because it has a simple structure and is inexpensive. In this case, a filter that allows the passage of gas but blocks the passage of liquid may be arranged at the gas-liquid interface in the container.
  • a liquid line may be connected to the bottom of the container and a valve may be provided in the middle thereof.
  • the condensed water stored in the container can be discharged to the outside of the gas production apparatus 1 via the liquid line by opening the valve.
  • the liquid line may be connected to the tank 30, which will be described later, to reuse the discharged condensed water.
  • the exhaust gas from which the condensed water has been removed by the gas-liquid separator can be configured to be supplied to the protector, for example.
  • the protector is provided with a substance that is a fine component contained in the exhaust gas and can capture a component (inactivating component) that reduces the activity of the reducing agent 4R by contact with the reducing agent 4R.
  • the substance in the protector reacts (captures) with the inactivating component to prevent the exhaust gas from reaching the reducing agent 4R in the reactors 4a and 4b.
  • it can be suppressed and protected (ie, prevent a decrease in activity). Therefore, it is possible to prevent or suppress the efficiency of conversion of carbon dioxide to carbon monoxide by the reducing agent 4R from being extremely lowered due to the adverse effect of the inactivating component.
  • Such a substance includes a substance having a composition contained in the reducing agent 4R and having a composition of reducing the activity of the reducing agent 4R by contact with an inactivating component, specifically, a metal oxide contained in the reducing agent 4R.
  • an inactivating component specifically, a metal oxide contained in the reducing agent 4R.
  • the same or similar metal oxides as can be used.
  • similar metal oxides have the same metal elements contained therein, but have different compositions, or different types of metal elements contained therein, but have the same group in the element periodic table. It refers to a certain metal oxide.
  • the inactivating component is preferably at least one selected from sulfur, mercury, sulfur compounds, halogen compounds, organic silicones, organic phosphorus and organic metal compounds, and at least one selected from sulfur and sulfur compounds. More preferably, it is a seed.
  • the substance may be any substance whose activity is reduced by the same component as the inactivating component of the reducing agent 4R, and metal oxides such as iron oxide and zinc oxide are excellent in capturing the inactivating component. Is preferable.
  • the protector has a structure in which a mesh material is arranged in a housing and particles of the above substance are placed on the mesh material, a honeycomb-shaped filter member composed of the above-mentioned substance, or a cylindrical or particle-like protector.
  • the structure may be such that the molded body is arranged.
  • the protector is arranged between the compression unit 6 (gas-liquid separator) and the exhaust gas heating unit 10, it is necessary to improve the efficiency of removing inactivated components while preventing deterioration of the above substances due to heat. Can be done.
  • the exhaust gas heating unit 10 heats the exhaust gas before being supplied to the reactors 4a and 4b. By preheating the exhaust gas before the reaction (before reduction) in the exhaust gas heating unit 10, the conversion (reduction) reaction of carbon dioxide to carbon monoxide by the reducing agent 4R is further promoted in the reactors 4a and 4b. be able to.
  • the exhaust gas heating unit 10 can be composed of, for example, an electric heater 101 and a heat exchanger (economizer) 102, as shown in FIG.
  • the heat exchanger 102 bends a part of the pipes constituting the gas line GL4 (see below) for discharging the gas (mixed gas) after passing through the reactors 4a and 4b, and becomes the pipes constituting the gas line GL1.
  • the heat of the high-temperature gas (mixed gas) after passing through the reactors 4a and 4b is used to heat the exhaust gas before being supplied to the reactors 4a and 4b by heat exchange. Can be effectively used.
  • the heat exchanger 102 includes, for example, a jacket type heat exchanger, a immersion coil type heat exchanger, a double tube type heat exchanger, a shell & tube type heat exchanger, a plate type heat exchanger, a spiral type heat exchanger, and the like. Can be configured as. Further, in the exhaust gas heating unit 10, either the electric heater 101 or the heat exchanger 102 may be omitted. In the exhaust gas heating unit 10, a combustion furnace or the like can be used instead of the electric heater 101. However, if the electric heater 101 is used, electric power (electrical energy) as renewable energy can be used as the power source thereof, so that the load on the environment can be reduced. As renewable energy, electric energy using at least one selected from solar power generation, wind power generation, hydroelectric power generation, wave power generation, tidal power generation, biomass power generation, geothermal power generation, solar heat and underground heat is used. It is possible.
  • renewable energy electric energy using at least one selected from solar power generation, wind power generation, hydroelectric power generation, wave power generation,
  • the exhaust gas line is branched from the gas line GL1 and the gas is branched at the end thereof.
  • a vent portion provided outside the manufacturing apparatus 1 may be connected.
  • a valve is preferably provided in the middle of the exhaust gas line. If the pressure in the gas production apparatus 1 (gas line GL1) rises more than necessary, a part of the exhaust gas is discharged (released) from the vent portion via the exhaust gas line by opening the valve. be able to. This makes it possible to prevent damage to the gas production apparatus 1 due to an increase in pressure.
  • the gas line GL2 is connected to the reducing gas supply unit 3 at one end thereof.
  • the gas line GL2 is connected to the inlet ports of the reactors 4a and 4b provided in the reaction unit 4 via the gas switching unit 8 and the two gas lines GL3a and GL3b, respectively.
  • the reducing gas supply unit 3 supplies a reducing gas containing a reducing substance that reduces the reducing agent 4R oxidized by contact with carbon dioxide.
  • the reduced gas supply unit 3 of the present embodiment is composed of a hydrogen generator that generates hydrogen by electrolysis of water, and a tank (reduced gas raw material storage unit) outside the gas production apparatus 1 that stores water in this hydrogen generator. 30 is connected.
  • the reducing gas containing hydrogen (reducing substance) supplied from the hydrogen generator (reducing gas supply unit 3) passes through the gas line GL2 and is supplied to the reactors 4a and 4b.
  • the hydrogen generator a large amount of hydrogen can be generated relatively inexpensively and easily. Further, there is an advantage that the condensed water generated in the gas production apparatus 1 can be reused. Since the hydrogen generator consumes a large amount of electric energy among the gas production apparatus 1, it is effective to use the electric power as the renewable energy as described above.
  • the hydrogen generator a device that generates by-product hydrogen can also be used.
  • the reducing gas containing by-product hydrogen is supplied to each of the reactors 4a and 4b.
  • the device for generating by-product hydrogen include a device for electrolyzing an aqueous sodium chloride solution, a device for steam reforming petroleum, a device for producing ammonia, and the like.
  • the gas line GL2 may be connected to the coke oven outside the gas production apparatus 1 via the connecting portion, and the exhaust gas from the coke oven may be used as the reducing gas.
  • the connecting portion constitutes the reducing gas supply portion.
  • a reducing gas heating unit 11 is provided in the middle of the gas line GL2.
  • the reducing gas heating unit 11 heats the reducing gas before being supplied to the reactors 4a and 4b.
  • the reduction (regeneration) reaction of the reducing agent 4R by the reducing gas in the reactors 4a and 4b can be further promoted.
  • the reducing gas heating unit 11 can be configured in the same manner as the exhaust gas heating unit 10.
  • the reduction gas heating unit 11 is preferably composed of only an electric heater, only a heat exchanger, and a combination of an electric heater and a heat exchanger, and is composed of only a heat exchanger and a combination of an electric heater and a heat exchanger. Is more preferable. If the reducing gas heating unit 11 is provided with a heat exchanger, the heat of the high-temperature gas (for example, a mixed gas) after passing through the reactors 4a and 4b is used before being supplied to the reactors 4a and 4b. Since the reducing gas is heated by heat exchange, the heat can be effectively used.
  • a mixed gas for example, a mixed gas
  • the exhaust gas is sent to the reactor 4a containing the reducing agent 4R before oxidation via the gas line GL3a.
  • the reducing gas can be supplied to the reactor 4b in which the reducing agent 4R after oxidation is housed via the gas line GL3b.
  • the reaction of the following formula 1 proceeds in the reactor 4a
  • the reaction of the following formula 2 proceeds in the reactor 4b.
  • the metal oxide contained in the reducing agent 4R is iron oxide (FeO x-1 ) is shown as an example.
  • Equation 1 CO 2 + FeO x-1 ⁇ CO + FeO x Equation 2: H 2 + FeO x ⁇ H 2 O + FeO x-1
  • the gas production apparatus 1 is a reducing agent heating unit that heats the reducing agent 4R when the reducing agent 4R is brought into contact with the exhaust gas or the reducing gas (that is, when the exhaust gas or the reducing gas reacts with the reducing agent 4R). It is preferable to further have (not shown in FIG. 1).
  • a reducing agent heating unit By providing such a reducing agent heating unit, the temperature in the reaction between the exhaust gas or the reducing gas and the reducing agent 4R is maintained at a high temperature, and the decrease in the conversion efficiency of carbon dioxide into carbon monoxide is suitably prevented or suppressed. , The regeneration of the reducing agent 4R by the reducing gas can be further promoted.
  • the reactions represented by the above formulas 1 and 2 may be exothermic reactions.
  • the gas production apparatus 1 has a reducing agent cooling unit that cools the reducing agent 4R instead of the reducing agent heating unit.
  • a reducing agent cooling unit By providing such a reducing agent cooling unit, deterioration of the reducing agent 4R is suitably prevented during the reaction between the exhaust gas or the reducing gas and the reducing agent 4R, and the conversion efficiency of carbon dioxide into carbon monoxide is improved. It is possible to suitably prevent or suppress the decrease and further promote the regeneration of the reducing agent 4R by the reducing gas.
  • the gas production apparatus 1 is provided with a reducing agent temperature control unit that adjusts the temperature of the reducing agent 4R depending on the type of the reducing agent 4R (exothermic reaction or endothermic reaction).
  • a reducing agent temperature control unit that adjusts the temperature of the reducing agent 4R depending on the type of the reducing agent 4R (exothermic reaction or endothermic reaction).
  • the suitable configuration of the reducing agent temperature control section will be described in detail later.
  • Branch gas lines GL4a and GL4b are connected to the outlet ports of the reactors 4a and 4b, respectively, and these branches at the gas merging portion J4 to form the gas line GL4. Further, valves (not shown) are provided in the middle of the branched gas lines GL4a and GL4b, if necessary. For example, by adjusting the opening degree of the valve, the passing speed of the exhaust gas and the reducing gas passing through the reactors 4a and 4b (that is, the processing speed of the exhaust gas by the reducing agent 4R and the processing speed of the reducing agent 4R by the reducing gas) can be adjusted. Can be set.
  • the reactor 4 is composed of the reactors 4a and 4b and the gas switching unit 8.
  • the gases mainly carbon monoxide and steam in this embodiment
  • the mixed gas merged gas
  • the gases Will pass through one gas line GL4 after being generated. Therefore, if the flow path switching state (valve open / closed state) of the gas switching unit 8 is changed and different reactions are performed in the reactors 4a and 4b, the mixed gas can be continuously produced, and finally. The generated gas can also be continuously produced. Further, since the same reaction is alternately repeated in the reactors 4a and 4b, the concentration of carbon monoxide contained in the mixed gas is stabilized, and as a result, the concentration of carbon monoxide contained in the produced gas is stabilized. It can also be turned into. Therefore, the gas production apparatus 1 (gas production system 100) described above can continuously and stably produce carbon monoxide from carbon dioxide, which is industrially advantageous.
  • the reactors 4a and 4b should be batch type. I have no choice but to do so. Therefore, the production time of carbon monoxide becomes long, the conversion efficiency is poor, and it is industrially disadvantageous. Further, the components of the gas discharged from each of the reactors 4a and 4b are different each time the supplied gas is switched. Therefore, the post-treatment process of the gas discharged from each of the reactors 4a and 4b becomes complicated. Here, it is usually preferable to adjust the concentration of carbon monoxide contained in the mixed gas to a specific range (a predetermined volume% with respect to the entire mixed gas).
  • this concentration is too low, it tends to be difficult to obtain a produced gas containing carbon monoxide at a high concentration, although it depends on the performance of the gas purification unit 9 described later. On the other hand, even if the concentration exceeds the upper limit of this concentration, no further increase in the effect of further increasing the concentration of carbon monoxide contained in the finally obtained product gas cannot be expected.
  • a generated gas discharging unit 40 for discharging the produced gas to the outside of the gas producing apparatus 1 is connected to the opposite ends of the reactors 4a and 4b of the gas line GL4. Further, a gas refining unit 9 is provided in the middle of the gas line GL4.
  • the gas purification unit 9 purifies carbon monoxide from the mixed gas and recovers the produced gas containing a high concentration of carbon monoxide. If the carbon monoxide concentration in the mixed gas is sufficiently high, the gas purification unit 9 may be omitted.
  • the gas purification unit 9 can be composed of, for example, at least one of a cooler, a gas-liquid separator, a gas separator, a separation membrane, and a scrubber (absorption tower).
  • the order of arrangement thereof is arbitrary, but when a cooler, a gas-liquid separator, and a gas separator are used in combination, it is preferable to arrange them in this order. In this case, the efficiency of purifying carbon monoxide from the mixed gas can be further increased.
  • the cooler cools the mixed gas. As a result, condensed water (liquid) is generated.
  • a cooler has the same configuration as the reactors 4a and 4b, which are jacket-type cooling devices in which a jacket for passing the refrigerant is arranged around the pipe (see FIG. 2), and the mixed gas is introduced into the pipe body. It can be configured to include a multi-tube type cooling device, an air fin cooler, etc., which allow the refrigerant to pass around each of them.
  • the gas-liquid separator separates the condensed water generated when the mixed gas is cooled by the cooler from the mixed gas.
  • the condensed water has an advantage that unnecessary gas components (particularly carbon dioxide) remaining in the mixed gas can be dissolved and removed.
  • the gas-liquid separator can be configured in the same manner as the gas-liquid separator of the fine component removing unit 7, and can preferably be configured as a simple container.
  • a filter that allows the passage of gas but blocks the passage of liquid may be arranged at the gas-liquid interface in the container.
  • a liquid line may be connected to the bottom of the container and a valve may be provided in the middle thereof. According to such a configuration, the condensed water stored in the container can be discharged (discharged) to the outside of the gas production apparatus 1 via the liquid line by opening the valve.
  • a drain trap on the downstream side of the valve in the middle of the liquid line.
  • a valve malfunction detection function and a redundancy measure when the valve malfunctions may be provided.
  • the liquid line may be connected to the tank 30 described above to reuse the discharged condensed water.
  • Gas separators include, for example, a low temperature separation type (deep cooling type) separator, a pressure swing adsorption (PSA) type separator, a membrane separation type separator, a temperature swing adsorption (TSA) type separator, and a metal ion.
  • PSA pressure swing adsorption
  • TSA temperature swing adsorption
  • a valve may be provided between the gas-liquid separator of the gas line GL4 and the gas separator. In this case, the processing speed of the mixed gas (production speed of the produced gas) can be adjusted by adjusting the opening degree of the valve.
  • the concentration of carbon monoxide contained in the mixed gas discharged from the gas-liquid separator is 75 to 90% by volume with respect to the entire mixed gas. Therefore, in a field where a production gas containing carbon monoxide at a relatively low concentration (75 to 90% by volume) can be used, carbon monoxide can be directly supplied to the next step without being purified from the mixed gas. That is, the gas separator can be omitted.
  • Such fields include, for example, the field of synthesizing valuable substances (for example, ethanol) by fermentation of the produced gas with a microorganism (for example, clostridium), the field of producing steel using the produced gas as a fuel or a reducing agent, and the like. Examples include the field of manufacturing electric devices and the field of synthesizing chemical products (phosgene, acetic acid, etc.) using carbon monoxide as a synthetic raw material.
  • the produced gas containing carbon monoxide at a high concentration is obtained by purifying carbon monoxide from the mixed gas.
  • Such fields include, for example, a field in which the produced gas is used as a reducing agent (blast furnace), a field in which the produced gas is used as a fuel to generate power by thermal power, a field in which a chemical product is produced using the produced gas as a raw material, and a field in which the produced gas is used as a fuel. Examples include the field of fuel cells used as fuel cells.
  • the exhaust gas passes through the oxygen removing device (concentration adjusting unit 5). As a result, oxygen is removed from the exhaust gas, and the concentration of carbon dioxide contained in the exhaust gas increases. [4] Next, the exhaust gas passes through the compression unit 6. As a result, the pressure of the exhaust gas rises. [5] Next, the exhaust gas passes through the fine component removing unit 7. As a result, the condensed water generated when the exhaust gas is compressed by the compression unit 6 and the inactivating component that reduces the activity of the reducing agent 4R are removed from the exhaust gas.
  • the exhaust gas passes through the exhaust gas heating unit 10. This heats the exhaust gas.
  • the exhaust gas is supplied to the reactor 4a.
  • carbon dioxide in the exhaust gas is reduced to carbon monoxide by the reducing agent 4R.
  • the reducing agent 4R is oxidized.
  • the heating temperature of the exhaust gas in the above step [6] is preferably 300 to 700 ° C, more preferably 450 to 700 ° C, further preferably 600 to 700 ° C, and 650 to 700 ° C. Is particularly preferred.
  • the heating temperature of the exhaust gas is set in the above range, for example, it is possible to prevent or suppress a rapid temperature drop of the reducing agent 4R due to an endothermic reaction when converting carbon dioxide into carbon monoxide.
  • the carbon dioxide reduction reaction can proceed more smoothly.
  • water (reduced gas raw material) is supplied from the tank 30 to the hydrogen generator (reduced gas supply unit 3) to generate hydrogen from the water.
  • the reducing gas containing hydrogen passes through the reducing gas heating unit 11. As a result, the reducing gas is heated.
  • the reducing gas is supplied to the reactor 4b.
  • the reducing agent 4R in the oxidized state is reduced (regenerated) by the reducing gas (hydrogen).
  • the heating temperature of the reducing gas in the above step [9] is preferably 300 to 700 ° C, more preferably 450 to 700 ° C, further preferably 600 to 700 ° C, and 650 to 700 ° C.
  • the heating temperature of the reducing gas is set in the above range, for example, it is possible to prevent or suppress a rapid temperature drop of the reducing agent 4R due to an endothermic reaction when reducing (regenerating) the reducing agent 4R in an oxidized state.
  • the reduction reaction of the reducing agent 4R in the reactor 4b can proceed more smoothly.
  • the heating temperature of the exhaust gas by the exhaust gas heating unit 10 is X [° C.] and the heating temperature of the reduced gas by the reducing gas heating unit 11 is Y [° C.],
  • the absolute value of the difference from 0 to 25) is preferably satisfied with the relationship of 0 to 25, more preferably satisfied with the relationship of 0 to 20, and further preferably satisfied with the relationship of 0 to 15.
  • the heating temperature X of the exhaust gas and the heating temperature Y of the reducing gas may be the same or slightly different.
  • X and Y are set so as to satisfy the above relationship, the conversion of carbon dioxide to carbon monoxide and the reduction of the reducing agent 4R by the reducing gas can proceed in a good balance.
  • the heating temperature X of the exhaust gas and the heating temperature Y of the reducing gas are different, the amount of heat required for the reduction reaction of the reducing agent 4R by the reducing gas is larger than the amount of heat required for the reduction reaction of carbon dioxide by the reducing agent 4R. Therefore, it is preferable to set the heating temperature Y of the reducing gas higher than the heating temperature X of the exhaust gas.
  • the switching timing of the gas line in the gas switching unit 8 (that is, the switching timing between the exhaust gas supplied to the reactors 4a and 4b and the reducing gas) is the condition I: a predetermined amount to the reactor 4a or 4b. It is preferable that the exhaust gas is supplied or the condition II: the conversion efficiency of carbon dioxide to carbon monoxide falls below a predetermined value.
  • the reactors 4a and 4b are switched before the efficiency of carbon dioxide conversion to carbon monoxide is significantly reduced, so that the concentration of carbon monoxide contained in the mixed gas is increased and stabilized. be able to.
  • gas concentration sensors may be arranged near the inlet and outlet ports of the reactors 4a and 4b, respectively. Based on the detection value of this gas concentration sensor, the conversion efficiency of carbon dioxide to carbon monoxide can be calculated.
  • the amount of exhaust gas supplied to the reactors 4a and 4b and the amount of reduced gas supplied to the reactors 4a and 4b can be determined. It is preferable to set it as close as possible. Specifically, when the amount of exhaust gas supplied to the reactors 4a and 4b is P [mL / min] and the amount of reduced gas supplied to the reactors 4a and 4b is Q [mL / min], P / Q. Is preferably satisfied with the relationship of 0.9 to 2, and more preferably satisfied with the relationship of 0.95 to 1.5.
  • the amount of exhaust gas supplied P is too large, the amount of carbon dioxide emitted from the reactors 4a and 4b increases without being converted to carbon monoxide, depending on the amount of the reducing agent 4R in the reactors 4a and 4b. Tend to do.
  • the predetermined amount under the above condition I is preferably 0.01 to 3 mol of carbon dioxide per 1 mol of the metal element having the largest proportion of the mass in the reducing agent 4R, and 0.1 to 2.5. More preferably, it is in the amount of moles.
  • the predetermined value under the above condition II is preferably 50 to 100%, more preferably 60 to 100%, and even more preferably 70 to 100%.
  • the upper limit of the predetermined value may be 95% or less, or 90% or less.
  • the reactors 4a and 4b can be switched before the efficiency of carbon dioxide conversion to carbon monoxide drops significantly, and as a result, the mixed gas containing a high concentration of carbon monoxide is stable. Therefore, it is also possible to produce a produced gas containing a high concentration of carbon monoxide.
  • the supply amount Q of the reducing gas (reducing substance) is preferably 0.1 to 3 mol, and 0.15 mol, per 1 mol of the metal element having the largest proportion of the mass in the reducing agent 4R. More preferably, the amount is ⁇ 2.5 mol. Even if the supply amount Q of the reducing gas is increased beyond the upper limit value, no further increase in the effect of reducing the reducing agent 4R in the oxidized state cannot be expected. On the other hand, if the supply amount Q of the reducing gas is too small, the reduction of the reducing agent 4R may be insufficient depending on the amount of hydrogen contained in the reducing gas. Further, the pressure of the reducing gas supplied to the reactors 4a and 4b may be atmospheric pressure or may be pressurized (similar to the exhaust gas).
  • the gases that have passed through the reactors 4a and 4b merge to form a mixed gas.
  • the temperature of the mixed gas is usually 600-650 ° C. If the temperature of the mixed gas at this point is in the above range, it means that the temperature in the reactors 4a and 4b is maintained at a sufficiently high temperature, and the conversion of carbon dioxide to carbon monoxide by the reducing agent 4R. Alternatively, it can be determined that the reduction of the reducing agent 4R with the reducing gas is proceeding efficiently.
  • the mixed gas is cooled to 100 to 300 ° C. by the time it reaches the gas purification unit 9.
  • the mixed gas passes through the gas refining unit 9.
  • the generated condensed water and carbon dioxide dissolved in the condensed water are removed.
  • carbon monoxide is purified from the mixed gas, and a produced gas containing a high concentration of carbon monoxide is obtained.
  • the temperature of the obtained produced gas is 20 to 50 ° C.
  • FIG. 4 is a schematic view showing the configuration of the reducing agent heating unit
  • FIG. 5 is a schematic diagram showing another configuration of the reducing agent heating unit.
  • the reducing agent heating unit 12 shown in FIG. 4 has a medium and a medium to be supplied to the space 43 defined by the plurality of tubular bodies 41 and the housing 42 in the multi-tube reactors 4a and 4b shown in FIG.
  • a transfer device 121 for transferring to the space 43 and a heating device 122 for heating the medium are provided.
  • the reducing agent heating unit 12 of this configuration example includes a circulating medium line ML1 connected to each of the reactors 4a and 4b, and the medium line ML1 is filled with a medium.
  • the medium line ML1 is branched in the middle, connected to the reactors 4a and 4b, and then merged again to become one.
  • a transfer device 121 and a heating device 122 are arranged in the middle of the integrated medium line ML1. According to such a configuration, the medium heated by the heating device 122 is supplied to the space 43 of the reactors 4a and 4b when circulating in the medium line ML1.
  • the reducing agent 4R is indirectly heated via the tubular body 41.
  • the heating temperatures of the reducing agents 4R of the two reactors 4a and 4b can be set to be substantially equal.
  • the heating temperature of the reducing agent 4R is preferably 300 to 700 ° C, more preferably 650 to 700 ° C. If the heating temperature is too high, the reducing agent 4R tends to deteriorate and its activity tends to decrease, depending on the type of metal oxide constituting the reducing agent 4R. On the other hand, if the heating temperature is too low, the time required to produce a produced gas containing carbon monoxide at a high concentration tends to be long.
  • the heating device 122 can be composed of only an electric heater, or can also be composed of an electric heater and a heat exchanger similar to that described in the exhaust gas heating unit 10. According to the latter configuration, the heat of the high-temperature gas after passing through the reactors 4a and 4b is used to heat the medium before being supplied to the reactors 4a and 4b by heat exchange, so that heat can be effectively used. Can be planned.
  • the transfer device 121 can be configured by a blower. Further, when a liquid is used as a medium, the transfer device 121 can be configured by a pump.
  • the reducing agent heating unit 12 may be configured with an electric heater instead of the configuration using a medium (heating gas).
  • the heating by the electric heater may be performed on the housing 42 of the reactors 4a and 4b, or may be performed separately on the tube 41 filled with the reducing agent 4R.
  • the reducing agent heating unit 12 shown in FIG. 5 includes a non-circulating medium line ML2, and is configured to use the atmosphere (gas) as the medium.
  • a transfer device 121 (blower), a first heat exchanger 123, and a heating device 124 composed of an electric heater are arranged in order from the air supply port side of the medium line ML2 to exhaust the atmosphere.
  • a second heat exchanger 125 is arranged on the outlet side. It is preferable that the first heat exchanger 123 and the second heat exchanger 125 each have the same configuration as the heat exchanger 102.
  • the first heat exchanger 123 is between the gas (for example, a mixed gas) after passing through the tube 41 of the reactors 4a and 4b and the atmosphere before supplying to the space 43 of the reactors 4a and 4b.
  • Heat exchange On the other hand, the second heat exchanger 125 exchanges heat between the atmosphere after passing through the space 43 of the reactors 4a and 4b and the exhaust gas before supplying to the reactors 4a and 4b.
  • Heat is used to heat the atmosphere (medium) or exhaust gas before being supplied to the reactors 4a and 4b by heat exchange using the heat of the high-temperature gas or atmosphere (medium) after passing through the reactors 4a and 4b.
  • the second heat exchanger 125 replaces the configuration of exchanging heat with the exhaust gas before being supplied to the reactors 4a and 4b, and heat is exchanged with the reducing gas before being supplied to the reactors 4a and 4b. It may be configured to be exchanged, or it may be configured to exchange heat with both the exhaust gas and the reducing gas before being supplied to the reactors 4a and 4b. Further, according to the configuration example shown in FIG. 5, since the temperature of the medium in contact with the transfer device 121 is lower than that of the configuration example shown in FIG. 4, it is possible to use a relatively inexpensive transfer device having low heat resistance. There are advantages.
  • the reducing agent heating unit may be configured to include an irradiation device that irradiates the reducing agent 4R with microwaves.
  • the reducing agent 4R can be heated to a target temperature in a relatively short time. Further, it is easy to uniformly heat not only the vicinity of the surface of the reducing agent 4R but also the central portion. Further, it is easy to precisely control the heating temperature of the reducing agent 4R. Therefore, if an irradiation device is used, the production efficiency of the generated gas can be further improved.
  • the irradiation device can be miniaturized as compared with the configurations shown in FIGS. 4 and 5. Further, in the case of microwave irradiation, only the vicinity of the surface of the reducing agent 4R can be locally (prioritically) raised to the target temperature. Therefore, when the reaction proceeds at a high temperature (in the case of an endothermic reaction), it is easy to increase the efficiency. In this case, since it is sufficient to input enough energy to raise the temperature only near the surface of the reducing agent 4R, the energy efficiency is also improved.
  • Microwave means an electromagnetic wave having a frequency of 300 MHz to 300 GHz, an ultra-high frequency wave (UHF) having a frequency of 300 to 3000 MHz, a centimeter wave (SHF) having a frequency of 3 to 30 GHz, a millimeter wave (EHF) having a frequency of 30 to 300 GHz, and a frequency 300. It is classified as a submillimeter wave (SHF) of ⁇ 3000 GHz.
  • ultra high frequency (UHF) is preferable as the microwave.
  • UHF ultra high frequency
  • the reducing agent 4R can be heated to a target temperature in a shorter time. When irradiating microwaves, measures against radio wave leakage in accordance with the Radio Law are taken appropriately.
  • the microwave irradiation may be performed continuously or intermittently (pulse-like).
  • the present inventors have found that continuous irradiation with microwaves further enhances the conversion efficiency of carbon dioxide into carbon monoxide and the regeneration (reduction) efficiency of the reducing agent 4R by the reducing gas. The reason is not always clear, but carbon dioxide contained in the exhaust gas supplied into the reactors 4a and 4b, hydrogen contained in the reducing gas and the reducing agent 4R are continuously irradiated with microwaves. It is thought that activation is a factor.
  • microwave irradiation when microwave irradiation is performed intermittently, only the energy required for the endothermic reaction during the conversion of carbon dioxide to carbon monoxide and the regeneration (reduction) of the reducing agent 4R with the reducing gas is compensated. As described above, it is sufficient to irradiate the microwave at a predetermined timing, so that the energy efficiency can be improved.
  • the heating temperature of the exhaust gas, the heating temperature of the reducing gas, and the heating temperature of the reducing agent 4R may be in the same range as described above, or may be different from the above range.
  • each of the above heating temperatures can be set to 300 to 700 ° C.
  • the irradiation device may be arranged inside the reactors 4a and 4b, or may be arranged outside. As described above, if the gas composition of the exhaust gas is deviated from the explosion range by the concentration adjusting unit 5, it is possible to suitably prevent the exhaust gas from becoming an ignition source regardless of the microwave irradiation conditions. .. Further, since electric energy is used as the power source of the irradiation device, there is an advantage that this electric energy can be easily switched to renewable energy.
  • the reducing agent temperature control unit can be configured as the reducing agent cooling unit.
  • the first heat exchanger 123 and the second heat exchanger 125 may be omitted, and the heating devices 122 and 124 may be replaced with cooling devices.
  • the cooling device include a jacket type cooling device, a multi-tube type cooling device, and the like. Also in this case, it is preferable that the cooling temperature (temperature after temperature adjustment) of the reducing agent 4R is in the same range as described above.
  • FIG. 6 is a schematic view showing a configuration in the vicinity of a connection portion (raw material gas supply portion) between the gas production apparatus of the present invention and the furnace.
  • the furnace 20 includes a chimney 21 that discharges exhaust gas to the atmosphere.
  • One end of the gas line 23 is connected to the branch portion 22 in the middle of the chimney 21 in the height direction. Further, the other end of the gas line 23 is connected to the connection portion 2 of the gas production apparatus 1.
  • a cooling unit 13 is provided between the connection unit 2 and the concentration adjusting unit 5.
  • the cooling unit 13 includes a cooling device 131 and a container 132 connected to the cooling device 131.
  • the cooling device 131 can be configured by a jacket type cooling device, a multi-tube type cooling device, or the like as described above. Since the exhaust gas supplied from the furnace 20 contains not only water vapor but also an oxidation gas component (SO x , HCl, etc.), the water vapor is condensed together with the oxidation gas component by cooling in the cooling unit 13, and the oxidation gas component is dissolved. It is preferable to remove it as condensed water (acidic aqueous solution).
  • an acidic aqueous solution is generated by cooling the exhaust gas with the cooling device 131, and the acidic aqueous solution is stored in the container 132 and separated from the exhaust gas.
  • a filter that allows the passage of gas but blocks the passage of liquid may be arranged at the gas-liquid interface in the container 132.
  • the separation distance (L1 in FIG. 6) between the branch portion 22 and the cooling device 131 is not particularly limited, but is preferably 10 m or less, and more preferably 1 to 5 m.
  • the separation distance L1 is set within the above range, it is possible to prevent the generation of condensed water (acidic aqueous solution) in which acid gas is dissolved at a place not intended for the gas line GL1 and to prevent the generation of condensed water (acidic aqueous solution) in the gas line GL1. Corrosion can be prevented more reliably.
  • the gas production system 100 when the gas production system 100 is installed in a cold region, for example, condensed water is generated in the middle of the gas line 23 depending on the separation distance L2 between the furnace 20 and the gas production apparatus 1, which leads to further freezing. Sometimes. This may damage the piping that constitutes the gas line 23. Therefore, in order to prevent such troubles, it is preferable to heat the exhaust gas in the gas line 23.
  • the heating temperature may be any temperature at which freezing does not occur, but is preferably an acid dew point temperature (for example, 120 ° C.) or higher, and more preferably 120 to 150 ° C.
  • a heating wire may be wound around the piping constituting the gas line 23 and arranged.
  • a resin lining pipe or the like made of a corrosion resistant resin material for example, a fluorine-based resin material
  • the container 132 may be omitted if necessary.
  • exhaust gas has been described as an example of the raw material gas, but as described above, the raw material gas is not particularly limited to the exhaust gas as long as it contains carbon dioxide. Therefore, in the above embodiment, various treatment conditions of the exhaust gas (including the pressure of pressurization by the compression unit 6, the heating temperature before supplying to the reactors 4a and 4b, the amount of supply to the reactors 4a and 4b, and the like). , And other raw material gases can be applied in the same manner.
  • the gas production method of the present embodiment is a method of producing a produced gas containing carbon monoxide by contacting the exhaust gas (raw material gas) with the reducing agent 4R, and I: reducing agent 4R is arranged inside.
  • the exhaust gas and the reducing gas were alternately brought into contact with the reducing agent 4R in each of the reactors 4a and 4b to convert carbon dioxide into carbon monoxide and then oxidized.
  • the reducing agent 4R is reduced, and III: the gases after passing through the reactors 4a and 4b are merged to generate a mixed gas, and IV: the mixed gas is used as it is, or carbon monoxide is purified from the mixed gas.
  • the produced gas produced by using the gas production apparatus 1 and the gas production system 100 usually has a carbon monoxide concentration of 60% by volume or more, preferably 75% by volume or more, and more preferably 90% by volume or more. ..
  • the generated gas as described above can be used in fields where valuable substances (eg, ethanol, etc.) are synthesized by fermentation with microorganisms (eg, clostridium, etc.), fields in which steel is produced by using it as a fuel or reducing agent, and electrical devices.
  • fields to manufacture chemicals phosgen, acetic acid, etc.
  • fields to use as a reducing agent blast furnace
  • fields to use as fuel to generate electricity by thermal power use as fuel It can be used in the field of fuel cells and the like.
  • FIG. 7 is a schematic view showing another embodiment of the gas production system of the present invention
  • FIG. 8 is a cross-sectional view schematically showing the configuration of the purifier of FIG. 7.
  • the gas production system 100 shown in FIG. 7 will be described mainly on the differences from the gas production system 100 shown in FIG.
  • the gas production system 100 shown in FIG. 7 further has refiners 14a and 14b provided in the middle of the branched gas lines GL4a and GL4b. That is, each of the purifiers 14a and 14b is connected to the downstream side of the corresponding reactors 4a and 4b, and the gas passing through the reactors 4a and 4b and the purifiers 14a and 14b sequentially merges at the gas confluence portion J4.
  • each of the refiners 14a and 14b is composed of a multi-tube refining device including a plurality of separation cylinders 141 and a housing (refiner main body) 142 accommodating the plurality of separation cylinders 141.
  • a multi-tube purification apparatus it is possible to sufficiently secure an opportunity for contact between the gas passing through the reactors 4a and 4b and the separation cylinder 141.
  • Each of the purifiers 14a and 14b has at least one of the separation of water (oxide of the reducing substance) and hydrogen (reducing substance) generated by contact with the reducing agent 4R and the separation of carbon monoxide and carbon dioxide. It is preferable that one is configured to be possible.
  • the separation cylinder 141 is configured so that its wall portion allows water (water vapor) or carbon monoxide to permeate and separates from hydrogen or carbon dioxide.
  • the water and carbon monoxide that have passed through the separation cylinder 141 are discharged from the refiners 14a and 14b to the branched gas lines GL4a and GL4b.
  • the reducing gas (unreacted hydrogen) and the exhaust gas (unreacted carbon dioxide) that have passed through the separation cylinder 141 are discharged to the gas lines GL14a and GL14b connected to the housing 142 (space 143).
  • These gas lines GL14a and GL14b may be connected in the middle of the gas line GL1 and the gas line GL2, respectively. This allows unreacted hydrogen and carbon dioxide to be reused.
  • the gas discharged to the branched gas lines GL4a and GL4b may contain gas components other than water or carbon monoxide, and the gas discharged to the gas lines GL14a and GL14b may also contain hydrogen or carbon dioxide. It may contain gas components other than carbon.
  • the separation of carbon monoxide and carbon dioxide and the separation of water and hydrogen cool the gas discharged from each reactor 4a and 4b by utilizing the difference in the temperature at which they condense (liquefy), respectively. It is also possible by doing. However, in this case, when the separated gas component is used in a high temperature state on the downstream side of the reactors 4a and 4b (for example, when it is used in the heat exchanger 102), it is necessary to heat it again. There is a waste of heat energy. On the other hand, according to the purifiers 14a and 14b, the gas component can be separated at a high temperature (for example, 200 to 500 ° C.), so that the temperature of the gas component after separation is unlikely to decrease.
  • a high temperature for example, 200 to 500 ° C.
  • a heating device for heating the separation cylinder 141 (for example, an irradiation device for irradiating the microwave) is provided. You may do so.
  • the separation cylinder 141 has heat resistance. Thereby, deterioration and deterioration of the separation cylinder 141 can be prevented. It is preferable that the separation cylinder 141 is made of a metal, an inorganic oxide, or a metal-organic framework (MOF). In this case, it is easy to impart excellent heat resistance to the separation cylinder 161.
  • the metal include titanium, aluminum, copper, nickel, chromium, cobalt, alloys containing these, and the like.
  • the inorganic oxide include silica and zeolite.
  • the metal-organic structure examples include a structure of zinc nitrate hydrate and terephthalate dianion, a structure of copper nitrate hydrate and trimesic acid trianion, and the like.
  • the separation cylinder 141 is preferably made of a porous material having a porosity of 80% or more.
  • the separation cylinder 141 is preferably composed of a porous body having continuous pores (pores penetrating the cylinder wall) in which adjacent pores communicate with each other. With the separation cylinder 141 having such a configuration, the transmittance of water or carbon monoxide can be increased, and the separation of water and hydrogen and / or the separation of carbon monoxide and carbon dioxide can be performed more smoothly and reliably. ..
  • the porosity of the separation cylinder 141 is not particularly limited, but is preferably 5 to 95%, more preferably 10 to 90%, and even more preferably 20 to 60%. This makes it possible to maintain a sufficiently high transmittance of water or carbon monoxide while preventing the mechanical strength of the separation cylinder 141 from being extremely lowered.
  • the shape of the separation cylinder 141 is not particularly limited, and examples thereof include a cylindrical shape, a quadrangular shape, and a square cylinder shape such as a hexagon.
  • the average pore diameter of the separation cylinder 141 is preferably 600 pm or less, and more preferably 400 to 500 pm. This makes it possible to further improve the separation efficiency of water and hydrogen.
  • the space 143 in the housing 142 may be depressurized or may be allowed to pass a carrier gas (sweep gas).
  • the carrier gas include an inert gas such as helium and argon.
  • the separation cylinder 141 is preferably hydrophilic. If the separation cylinder 141 has hydrophilicity, the affinity of water with respect to the separation cylinder 141 is enhanced, and it becomes easier for water to permeate the separation cylinder 141 more smoothly.
  • a method of imparting hydrophilicity to the separation cylinder 141 a method of changing the ratio of metal elements in the inorganic oxide (for example, increasing the Al / Si ratio) to improve the polarity of the separation cylinder 141, the separation cylinder 141.
  • the separation cylinder 141 when the separation of carbon monoxide and carbon dioxide is prioritized, and when both the separation of water and hydrogen and the separation of carbon monoxide and carbon dioxide are performed at the same time, the separation cylinder is used.
  • the constituent materials of 141, the pore ratio, the average pore diameter, the degree of hydrophilicity or hydrophobicity, the surface potential, and the like may be appropriately combined and set.
  • the refiner may be provided in the middle of the gas line GL4 between the gas confluence unit J4 and the gas purification unit 9. Further, when the refiners 14a and 14b are provided, the gas purification unit 9 may be omitted.
  • the present invention is not limited thereto.
  • the gas production apparatus and the gas production system of the present invention may each have any other additional configuration with respect to the above embodiment, and are replaced with any configuration exhibiting the same function. However, some configurations may be omitted. Further, in the gas production method of the present invention, any desired step may be added to the above embodiment.
  • a gas containing hydrogen as a reducing gas has been described as a representative, but the reducing gas includes a hydrocarbon (for example, methane, ethane, acetylene, etc.) as a reducing substance instead of hydrogen or together with hydrogen. And a gas containing at least one selected from ammonia can also be used.
  • the heat exchanger having the configuration of exchanging heat between the exhaust gas (raw material gas), the reducing gas or the medium for heating before being supplied to the reactor and the mixed gas has been described, but each reaction has been described.
  • a heat exchanger having a configuration that exchanges heat with the gas discharged from the vessel and before being made into a mixed gas may be adopted.
  • Cooling unit 131 ... Cooling device, 132 ... Container 14a, 14b ... Purifier 141 ... Separation cylinder, 142 ... Housing, 143 ... Space 20 ... Furnace 21 ... Chimney, 22 ... Branching part, 23 ... Gas line 30 ... Tank 40 ... Generated gas discharge part GL1 ... Gas line GL2 ... Gas line GL3a, GL3b ... Gas line GL4 ... Gas line GL4a, GL4b ... Branch gas line, J4 ... Gas confluence part GL14a, GL14b ... Gas line L1 ... Separation distance L2... Separation distance

Abstract

[Problem] To provide a gas production apparatus and a gas production system whereby it becomes possible to continuously and stably produce a product gas containing carbon monoxide from a raw material gas containing carbon dioxide. [Solution] The gas production apparatus 1 is an apparatus for producing a product gas containing carbon monoxide by bringing a raw material gas containing carbon dioxide into contact with a reducing agent comprising a metal oxide capable of reducing carbon dioxide. The gas production apparatus 1 is provided with a plurality of reactors 4a, 4b and a reducing agent placed in each of the reactors 4a,4b, is also provided with a reaction unit 4 by which the raw material gas and a reducing gas to be supplied to each of the reactors 4a, 4b can be switched to each other, and is configured such that, when a predetermined amount of the raw material gas is supplied to each of the reactors 4a, 4b or when the efficiency of conversion of carbon dioxide to carbon monoxide becomes smaller than a predetermined value, the raw material gas and the reducing gas to be supplied to each of the reactors 4a, 4b are switched to each other.

Description

ガス製造装置、ガス製造システムおよびガス製造方法Gas production equipment, gas production system and gas production method
　本発明は、ガス製造装置、ガス製造システムおよびガス製造方法に関する。 The present invention relates to a gas production apparatus, a gas production system, and a gas production method.
　近年、温室効果ガスの一種である二酸化炭素（ＣＯ２）は、その大気中の濃度が上昇を続けている。大気中の二酸化炭素の濃度の上昇は、地球温暖化を助長する。したがって、大気中に放出される二酸化炭素を回収することは重要であり、さらに回収した二酸化炭素を有価物質に変換して再利用できれば、炭素循環社会を実現することができる。
　また、地球規模の施策としても、気候変動に関する国際連合枠組条約の京都議定書にもあるように、地球温暖化の原因となる二酸化炭素について、先進国における削減率を、１９９０年を基準として各国別に定め、共同で約束期間内に削減目標値を達成することが定められている。 In recent years, the concentration of carbon dioxide (CO 2 ), which is a kind of greenhouse gas, has been increasing in the atmosphere. Increased concentrations of carbon dioxide in the atmosphere contribute to global warming. Therefore, it is important to recover the carbon dioxide released into the atmosphere, and if the recovered carbon dioxide can be converted into valuable substances and reused, a carbon cycle society can be realized.
In addition, as a global measure, as stated in the Kyoto Protocol of the United Nations Framework Convention on Climate Change, the reduction rate of carbon dioxide, which causes global warming, in developed countries is set for each country based on 1990. It is stipulated that the reduction target should be achieved jointly within the promised period.
　その削減目標を達成するため、製鉄所、精錬所または火力発電所から発生した二酸化炭素を含む排気ガスも対象となっており、これらの業界における二酸化炭素の削減に関して、様々な技術改良が行われている。かかる技術の一例としては、ＣＯ２回収・貯留（ＣＣＳ）が挙げられる。しかしながら、この技術では、貯留という物理的な限界があり、根本的な解決策とはなっていない。
　その他、例えば、特許文献１には、二酸化炭素から有価物質に変換する技術が開示されている。具体的には、ジルコニウムを含む酸化セリウムを用いて、二酸化炭素から一酸化炭素を製造する製造装置が開示されている。 Exhaust gases, including carbon dioxide, generated from steel mills, smelters or thermal power plants are also targeted to achieve that reduction target, and various technological improvements have been made to reduce carbon dioxide in these industries. ing. An example of such a technique is CO 2 capture and storage (CCS). However, this technology has the physical limitation of storage and is not a fundamental solution.
In addition, for example, Patent Document 1 discloses a technique for converting carbon dioxide into a valuable substance. Specifically, a manufacturing apparatus for producing carbon monoxide from carbon dioxide using cerium oxide containing zirconium is disclosed.
特許５８５８９２６号Patent No. 5858926
　しかしながら、発明者らの検討によると、特許文献１に記載の発明は、二酸化炭素から一酸化炭素を効果的に変換する金属酸化物を特定する発明である。特許文献１には、一酸化炭素の製造条件や製造装置においても、図にも示されているように概念的または一般的な情報が開示されるのみであり、工業的に一酸化炭素を製造するには、更なる技術改良が必要であることがわかった。
　そこで、本発明の目的は、二酸化炭素を含む原料ガスから、連続かつ安定して、一酸化炭素を含む生成ガスを製造することができるガス製造装置（すなわち、工業的に有利な製造装置）、ガス製造システムおよびガス製造方法を提供することにある。 However, according to the studies by the inventors, the invention described in Patent Document 1 is an invention for specifying a metal oxide that effectively converts carbon monoxide from carbon dioxide. Patent Document 1 only discloses conceptual or general information as shown in the drawings in terms of carbon monoxide production conditions and production equipment, and industrially produces carbon monoxide. It turned out that further technical improvement was necessary for this.
Therefore, an object of the present invention is a gas production apparatus (that is, an industrially advantageous production apparatus) capable of continuously and stably producing a produced gas containing carbon monoxide from a raw material gas containing carbon dioxide. To provide a gas production system and a gas production method.
　このような目的は、下記の本発明により達成される。 Such an object is achieved by the following invention.
　（１）　本発明のガス製造装置は、二酸化炭素を含む原料ガスと、前記二酸化炭素を還元する金属酸化物を含む還元剤とを接触させて、一酸化炭素を含む生成ガスを製造するガス製造装置であって、
　前記原料ガスを供給する原料ガス供給部と、
　前記二酸化炭素との接触により酸化された前記還元剤を還元する還元物質を含む還元ガスを供給する還元ガス供給部と、
　前記原料ガス供給部および前記還元ガス供給部にそれぞれ接続された複数の反応器と、前記反応器内に配置された前記還元剤とを備え、各前記反応器に供給する前記原料ガスと前記還元ガスとを切換可能な反応部とを有し、
　前記反応器を通過した後のガス同士を合流させて、混合ガスを生成するガス合流部とを有し、
　前記反応器へ所定の量の前記原料ガスを供給したとき、または、前記二酸化炭素の前記一酸化炭素への変換効率が所定の値を下回ったとき、各前記反応器に供給する前記原料ガスと前記還元ガスとを切り換えるように構成したことを特徴とする。 (1) The gas production apparatus of the present invention is a gas production device that produces a produced gas containing carbon monoxide by contacting a raw material gas containing carbon dioxide with a reducing agent containing the metal oxide that reduces carbon dioxide. It ’s a device,
The raw material gas supply unit that supplies the raw material gas and
A reducing gas supply unit that supplies a reducing gas containing a reducing substance that reduces the reducing agent oxidized by contact with carbon dioxide, and a reducing gas supply unit.
A plurality of reactors connected to the raw material gas supply unit and the reducing gas supply unit, and the reducing agent arranged in the reactor are provided, and the raw material gas and the reduction are supplied to each of the reactors. It has a reaction unit that can switch between gas and gas.
It has a gas merging portion that merges the gases after passing through the reactor to generate a mixed gas.
When a predetermined amount of the raw material gas is supplied to the reactor, or when the efficiency of converting carbon dioxide to carbon monoxide falls below a predetermined value, the raw material gas supplied to each of the reactors is used. It is characterized in that it is configured to switch with the reducing gas.
　（２）　本発明のガス製造装置では、前記反応器への前記原料ガスの供給量をＰ［ｍＬ／分］とし、前記反応器への前記還元ガスの供給量をＱ［ｍＬ／分］としたとき、Ｐ／Ｑが０．９～２なる関係を満足することが好ましい。
　（３）　本発明のガス製造装置では、前記所定の量は、前記還元剤に占める質量の割合が最も多い金属元素１モル当たり、前記二酸化炭素が０．０１～３モルの量であることが好ましい。
　（４）　本発明のガス製造装置では、前記所定の値は、５０～１００％であることが好ましい。 (2) In the gas production apparatus of the present invention, the supply amount of the raw material gas to the reactor is P [mL / min], and the supply amount of the reducing gas to the reactor is Q [mL / min]. When this is done, it is preferable to satisfy the relationship in which P / Q is 0.9 to 2.
(3) In the gas production apparatus of the present invention, the predetermined amount may be 0.01 to 3 mol of carbon dioxide per 1 mol of the metal element having the largest mass ratio in the reducing agent. preferable.
(4) In the gas production apparatus of the present invention, the predetermined value is preferably 50 to 100%.
　（５）　本発明のガス製造装置は、さらに、前記混合ガスと、前記反応器に供給する前の前記原料ガスとの間で熱交換する熱交換器を有することが好ましい。
　（６）　本発明のガス製造装置では、前記金属酸化物は、第３族～第１２族に属する金属元素から選択される少なくとも１種を含有することが好ましい。
　（７）　本発明のガス製造システムは、
　二酸化炭素を含む原料ガスを生成する原料ガス生成部と、
　本発明のガス製造装置とを備え、
　前記ガス製造装置が、前記原料ガス供給部を介して前記原料ガス生成部に接続されていることを特徴とする。 (5) It is preferable that the gas production apparatus of the present invention further has a heat exchanger that exchanges heat between the mixed gas and the raw material gas before being supplied to the reactor.
(6) In the gas production apparatus of the present invention, the metal oxide preferably contains at least one selected from the metal elements belonging to Group 3 to Group 12.
(7) The gas production system of the present invention is
A raw material gas generator that generates raw material gas containing carbon dioxide,
Equipped with the gas production apparatus of the present invention
The gas production apparatus is connected to the raw material gas generation unit via the raw material gas supply unit.
　（８）　本発明のガス製造方法は、二酸化炭素を含む原料ガスと、前記二酸化炭素を還元する金属酸化物を含む還元剤とを接触させて、一酸化炭素を含む生成ガスを製造するガス製造方法であって、
　前記還元剤を内部に配置した複数の反応器と、前記原料ガスと、前記二酸化炭素との接触により酸化された前記還元剤を還元する還元物質を含む還元ガスとを準備し、
　前記原料ガスと前記還元ガスとを供給する前記反応器を切り換えることにより、各前記反応器内において前記還元剤に前記原料ガスと前記還元ガスとを交互に接触させて、前記二酸化炭素を前記一酸化炭素に変換した後、前記酸化された還元剤を還元し、
　前記反応器を通過した後のガス同士を合流させて、混合ガスを生成し、
　前記混合ガスをそのまま、または、前記混合ガスから前記一酸化炭素を精製することにより、前記生成ガスとして回収するのに際して、
　前記反応器へ所定の量の前記原料ガスを供給したとき、または、前記二酸化炭素の前記一酸化炭素への変換効率が所定の値を下回ったとき、各前記反応器に供給する前記原料ガスと前記還元ガスとを切り換えることを特徴とする。 (8) In the gas production method of the present invention, a raw material gas containing carbon dioxide is brought into contact with a reducing agent containing a metal oxide that reduces carbon dioxide to produce a gas containing carbon monoxide. It ’s a method,
A plurality of reactors in which the reducing agent is arranged, a reducing gas containing the raw material gas and a reducing substance that reduces the reducing agent oxidized by contact with the carbon dioxide are prepared.
By switching the reactor that supplies the raw material gas and the reducing gas, the raw material gas and the reducing gas are alternately brought into contact with the reducing agent in each of the reactors, and the carbon dioxide is brought into the one. After converting to carbon oxide, the oxidized reducing agent is reduced to reduce it.
The gases after passing through the reactor are merged to generate a mixed gas.
When recovering the mixed gas as it is or by purifying the carbon monoxide from the mixed gas as the produced gas.
When a predetermined amount of the raw material gas is supplied to the reactor, or when the efficiency of converting carbon dioxide to carbon monoxide falls below a predetermined value, the raw material gas supplied to each of the reactors is used. It is characterized by switching from the reducing gas.
　本発明によれば、二酸化炭素を含む原料ガスから、効率よくかつ連続して、一酸化炭素を含む生成ガスを製造することができる。特に、本発明では、反応器に供給する原料ガスと還元ガスとの切換タイミングを調整することにより、上記効果をより向上させることができる。 According to the present invention, a produced gas containing carbon monoxide can be efficiently and continuously produced from a raw material gas containing carbon dioxide. In particular, in the present invention, the above effect can be further improved by adjusting the switching timing between the raw material gas supplied to the reactor and the reducing gas.
本発明のガス製造システムの一実施形態を示す概略図である。It is a schematic diagram which shows one Embodiment of the gas production system of this invention. 図１の反応器の構成を模式的に示す断面図である。It is sectional drawing which shows typically the structure of the reactor of FIG. 図１の排ガス加熱部の構成を示す概略図である。It is a schematic diagram which shows the structure of the exhaust gas heating part of FIG. 還元剤加熱部の構成を示す概略図である。It is a schematic diagram which shows the structure of the reducing agent heating part. 還元剤加熱部の他の構成を示す概略図である。It is a schematic diagram which shows the other structure of the reducing agent heating part. 本発明のガス製造装置と炉との接続部付近の構成を示す概略図である。It is a schematic diagram which shows the structure of the vicinity of the connection part between the gas production apparatus of this invention, and a furnace. 本発明のガス製造システムの他の実施形態を示す概略図である。It is a schematic diagram which shows the other embodiment of the gas production system of this invention. 図７の精製器の構成を模式的に示す断面図である。It is sectional drawing which shows typically the structure of the refiner of FIG.
　以下、本発明のガス製造装置、ガス製造システムおよびガス製造方法について、添付図面に示す好適実施形態に基づいて詳細に説明する。
　図１は、本発明のガス製造システムの一実施形態を示す概略図であり、図２は、図１の反応器の構成を模式的に示す断面図であり、図３は、図１の排ガス加熱部の構成を示す概略図である。
　図１に示すガス製造システム１００は、二酸化炭素を含む排ガス（原料ガス）を生成する炉（原料ガス生成部）２０と、接続部２を介して炉２０に接続されたガス製造装置１とを備えている。
　なお、本明細書中では、ガスの流れ方向に対して上流側を単に「上流側」、下流側を単に「下流側」とも記載する。 Hereinafter, the gas production apparatus, the gas production system, and the gas production method of the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings.
1 is a schematic view showing an embodiment of the gas production system of the present invention, FIG. 2 is a cross-sectional view schematically showing the configuration of the reactor of FIG. 1, and FIG. 3 is an exhaust gas of FIG. It is a schematic diagram which shows the structure of the heating part.
The gas production system 100 shown in FIG. 1 comprises a furnace (raw material gas generation unit) 20 that generates exhaust gas (raw material gas) containing carbon dioxide, and a gas production apparatus 1 connected to the furnace 20 via a connection unit 2. I have.
In the present specification, the upstream side with respect to the gas flow direction is also simply referred to as “upstream side”, and the downstream side is simply referred to as “downstream side”.
　炉２０としては、特に限定されないが、例えば、製鉄所、精錬所または火力発電所に付属する炉であり、好ましくは燃焼炉、高炉、転炉等が挙げられる。炉２０では、内容物の燃焼、溶融、精錬等の際に、排ガスが生成（発生）する。
　ゴミ焼却場にける燃焼炉（焼却炉）の場合、内容物（廃棄物）としては、例えば、プラスチック廃棄物、生ゴミ、都市廃棄物（ＭＳＷ）、廃棄タイヤ、バイオマス廃棄物、家庭ゴミ（布団、紙類）、建築部材等が挙げられる。なお、これらの廃棄物は、１種を単独で含んでいても、２種以上を含んでいてもよい。 The furnace 20 is not particularly limited, but is, for example, a furnace attached to a steel mill, a smelter, or a thermal power plant, and preferably includes a combustion furnace, a blast furnace, a converter, and the like. In the furnace 20, exhaust gas is generated (generated) when the contents are burned, melted, refined, or the like.
In the case of a combustion furnace (incinerator) in a garbage incinerator, the contents (waste) include, for example, plastic waste, swill, urban waste (MSW), waste tires, biomass waste, and household waste (futon). , Paper), building materials, etc. In addition, these wastes may contain 1 type alone or 2 or more types.
　排ガスは、通常、二酸化炭素に加えて、窒素、酸素、一酸化炭素、水蒸気、メタン等の他のガス成分を含む。排ガス中に含まれる二酸化炭素の濃度は、特に限定されないが、生成ガスの製造コスト（一酸化炭素への変換効率）を考慮すると、１体積％以上が好ましく、５体積％以上がより好ましい。
　ゴミ焼却場にける燃焼炉からの排ガスの場合、二酸化炭素が５～１５体積％、窒素が６０～７０体積％、酸素が５～１０体積％、水蒸気が１５～２５体積％で含まれる。 Exhaust gas usually contains carbon dioxide as well as other gas components such as nitrogen, oxygen, carbon monoxide, water vapor and methane. The concentration of carbon dioxide contained in the exhaust gas is not particularly limited, but is preferably 1% by volume or more, more preferably 5% by volume or more, in consideration of the production cost of the produced gas (efficiency of conversion to carbon monoxide).
In the case of exhaust gas from a combustion furnace in a garbage incinerator, carbon dioxide is contained in an amount of 5 to 15% by volume, nitrogen is contained in an amount of 60 to 70% by volume, oxygen is contained in an amount of 5 to 10% by volume, and water vapor is contained in an amount of 15 to 25% by volume.
　高炉からの排ガス（高炉ガス）は、高炉において銑鉄を製造する際に発生するガスであり、二酸化炭素が１０～１５体積％、窒素が５５～６０体積％、一酸化炭素が２５～３０体積％、水素が１～５体積％で含まれる。
　また、転炉からの排ガス（転炉ガス）は、転炉において鋼を製造する際に発生するガスであり、二酸化炭素が１５～２０体積％、一酸化炭素が５０～６０体積％、窒素が１５～２５体積％、水素が１～５体積％で含まれる。
　なお、原料ガスには、排ガスに限らず、二酸化炭素を１００体積％で含む純ガスを使用してもよい。 The exhaust gas from the blast furnace (blast furnace gas) is a gas generated when pig iron is produced in the blast furnace, and carbon dioxide is 10 to 15% by volume, nitrogen is 55 to 60% by volume, and carbon monoxide is 25 to 30% by volume. , Hydrogen is contained in 1-5% by volume.
The exhaust gas (converter gas) from the converter is a gas generated when steel is manufactured in the converter, and carbon dioxide is 15 to 20% by volume, carbon monoxide is 50 to 60% by volume, and nitrogen is. It contains 15 to 25% by volume and 1 to 5% by volume of hydrogen.
The raw material gas is not limited to the exhaust gas, and a pure gas containing 100% by volume of carbon dioxide may be used.
　ただし、原料ガスとして排ガスを使用すれば、従来、大気中に排出していた二酸化炭素を有効利用することができ、環境への負荷を低減することができる。これらの中でも、炭素循環という観点からは、製鉄所または精錬所で発生した二酸化炭素を含む排ガスが好ましい。
　また、高炉ガスや転炉ガスは、炉から排出された未処理のガスをそのまま使用してもよく、例えば、一酸化炭素等を除去する処理を施した後の処理済みガスを使用してもよい。未処理の高炉ガスおよび転炉ガスは、それぞれ上述のようなガス組成であり、処理済みガスは、燃焼炉からの排ガスで示したガス組成に近いガス組成となる。本明細書では、以上のようなガス（ガス製造装置１に供給される前のガス）をいずれも排ガスと呼ぶ。 However, if exhaust gas is used as the raw material gas, carbon dioxide conventionally emitted into the atmosphere can be effectively used, and the burden on the environment can be reduced. Among these, from the viewpoint of carbon cycle, exhaust gas containing carbon dioxide generated in a steel mill or a refinery is preferable.
Further, as the blast furnace gas or the linz-donaw gas, the untreated gas discharged from the furnace may be used as it is, or for example, the treated gas after being treated to remove carbon monoxide or the like may be used. good. The untreated blast furnace gas and the linz-Donaw gas each have a gas composition as described above, and the treated gas has a gas composition close to the gas composition shown in the exhaust gas from the combustion furnace. In the present specification, any of the above gases (gas before being supplied to the gas production apparatus 1) is referred to as exhaust gas.
　＜全体構成＞
　ガス製造装置１は、炉２０から排出され、接続部２を介して供給される排ガス（二酸化炭素を含む原料ガス）と、排ガス中に含まれる二酸化炭素を還元する金属酸化物を含む還元剤とを接触させて、一酸化炭素を含む生成ガス（合成ガス）を製造する。
　ガス製造装置１は、主に、接続部２と、還元ガス供給部３と、２つの反応器４ａ、４ｂと、接続部２と各反応器４ａ、４ｂとを接続するガスラインＧＬ１と、還元ガス供給部３と各反応器４ａ、４ｂとを接続するガスラインＧＬ２と、各反応器４ａ、４ｂに接続されたガスラインＧＬ４とを有している。
　本実施形態では、接続部２が、排ガスを反応器４ａ、４ｂに供給する原料ガス供給部を構成している。
　なお、必要に応じて、ガスラインＧＬ１、ガスラインＧＬ２およびガスラインＧＬ４の途中の所定の箇所には、ガスを移送するためのポンプを配置してもよい。例えば、後述する圧縮部６で排ガスの圧力を比較的低く調整する場合には、ポンプを配置することにより、ガス製造装置１内でガスを円滑に移送することができる。 <Overall configuration>
The gas production apparatus 1 includes an exhaust gas (raw material gas containing carbon dioxide) discharged from the furnace 20 and supplied via the connection portion 2, and a reducing agent containing a metal oxide that reduces carbon dioxide contained in the exhaust gas. To produce a produced gas (synthetic gas) containing carbon monoxide.
The gas production apparatus 1 mainly includes a connection unit 2, a reducing gas supply unit 3, two reactors 4a and 4b, a gas line GL1 connecting the connection unit 2 and the reactors 4a and 4b, and reduction. It has a gas line GL2 connecting the gas supply unit 3 and the reactors 4a and 4b, and a gas line GL4 connected to the reactors 4a and 4b.
In the present embodiment, the connection unit 2 constitutes a raw material gas supply unit that supplies exhaust gas to the reactors 4a and 4b.
If necessary, a pump for transferring gas may be arranged at a predetermined position in the middle of the gas line GL1, the gas line GL2, and the gas line GL4. For example, when the pressure of the exhaust gas is adjusted to be relatively low by the compression unit 6 described later, the gas can be smoothly transferred in the gas production apparatus 1 by arranging the pump.
　ガスラインＧＬ１は、その一端部において接続部２に接続されている。一方、ガスラインＧＬ１は、その他端部において、ガス切換部８および２つのガスラインＧＬ３ａ、ＧＬ３ｂを介して、それぞれ反応部４が備える反応器４ａ、４ｂの入口ポートに接続されている。
　かかる構成により、炉２０から接続部２を介して供給された排ガスは、ガスラインＧＬ１を通過して、各反応器４ａ、４ｂに供給される。
　ガス切換部８は、例えば、分岐ガスラインと、この分岐ガスラインの途中に設けられたバルブのような流路開閉機構とを含んで構成することができる。 The gas line GL1 is connected to the connecting portion 2 at one end thereof. On the other hand, the gas line GL1 is connected to the inlet ports of the reactors 4a and 4b provided in the reaction unit 4 via the gas switching unit 8 and the two gas lines GL3a and GL3b at the other end.
With this configuration, the exhaust gas supplied from the furnace 20 via the connection portion 2 passes through the gas line GL1 and is supplied to the reactors 4a and 4b.
The gas switching unit 8 can be configured to include, for example, a branched gas line and a flow path opening / closing mechanism such as a valve provided in the middle of the branched gas line.
　各反応器４ａ、４ｂは、図２に示すように、還元剤４Ｒをそれぞれ充填した複数の管体４１と、複数の管体４１を収納したハウジング４２とを備える多管式の反応装置（固定層式の反応装置）で構成されている。かかる多管式の反応装置によれば、還元剤４Ｒと排ガスおよび還元ガスとの接触の機会を十分に確保することができる。その結果、生成ガスの製造効率を高めることができる。
　本実施形態の還元剤４Ｒは、例えば、粒子状（顆粒状）、鱗片状、ペレット状等であることが好ましい。かかる形状の還元剤４Ｒであれば、管体４１への充填効率を高めることができ、管体４１内に供給されるガスとの接触面積をより増大させることができる。
　還元剤４Ｒが粒子状である場合、その体積平均粒径は、特に限定されないが、１～５０ｍｍであることが好ましく、３～３０ｍｍであることがより好ましい。この場合、還元剤４Ｒと排ガス（二酸化炭素）との接触面積をさらに高め、二酸化炭素の一酸化炭素への変換効率をより向上させることができる。同様に、還元物質を含む還元ガスによる還元剤４Ｒの再生（還元）もより効率よく行うことができる。
　粒子状の還元剤４Ｒは、より球形度が高まることから、転動造粒により製造された成形体であることが好ましい。 As shown in FIG. 2, each reactor 4a and 4b is a multi-tube reactor (fixed) including a plurality of tubular bodies 41 each filled with a reducing agent 4R and a housing 42 containing the plurality of tubular bodies 41. It is composed of a layered reactor). According to such a multi-tube reactor, it is possible to sufficiently secure an opportunity for contact between the reducing agent 4R and the exhaust gas and the reducing gas. As a result, the production efficiency of the produced gas can be improved.
The reducing agent 4R of the present embodiment is preferably in the form of particles (granule), scales, pellets, or the like. With the reducing agent 4R having such a shape, the filling efficiency into the tube 41 can be increased, and the contact area with the gas supplied into the tube 41 can be further increased.
When the reducing agent 4R is in the form of particles, its volume average particle size is not particularly limited, but is preferably 1 to 50 mm, more preferably 3 to 30 mm. In this case, the contact area between the reducing agent 4R and the exhaust gas (carbon dioxide) can be further increased, and the conversion efficiency of carbon dioxide into carbon monoxide can be further improved. Similarly, the regeneration (reduction) of the reducing agent 4R with a reducing gas containing a reducing substance can be performed more efficiently.
Since the particulate reducing agent 4R has a higher sphericity, it is preferably a molded product produced by rolling granulation.
　また、還元剤４Ｒは、担体に担持させるようにしてもよい。担体の構成材料としては、排ガス（原料ガス）や反応条件等に応じて変性し難いものであればよく、特に限定されないが、例えば、炭素材料（グラファイト、グラフェン等）、ゼオライト、モンモリロナイト、ＳｉＯ２、ＺｒＯ２、ＴｉＯ２、Ｖ２Ｏ５、ＭｇＯ、アルミナ（Ａｌ２Ｏ３）、シリカ、および、それら材料の複合酸化物等が挙げられる。これらの中でも、ゼオライト、モンモリロナイト、ＳｉＯ２、ＺｒＯ２、ＴｉＯ２、Ｖ２Ｏ５、ＭｇＯ、アルミナ（Ａｌ２Ｏ３）、シリカ、および、それら材料の複合酸化物が好ましい。かかる材料で構成される担体は、還元剤４Ｒの反応に悪影響を及ぼさず、還元剤４Ｒの担持能に優れる点で好ましい。ここで、担体は、還元剤４Ｒの反応には関与せず、還元剤４Ｒを単に支持（保持）する。かかる形態の一例としては、担体の表面の少なくとも一部を還元剤４Ｒで被覆する構成が挙げられる。 Further, the reducing agent 4R may be supported on a carrier. The constituent material of the carrier may be any material that is not easily modified depending on the exhaust gas (raw material gas), reaction conditions, etc., and is not particularly limited. For example, carbon material (graphene, graphene, etc.), zeolite, montmorillonite, SiO 2 , ZrO 2 , TiO 2 , V 2 O 5 , MgO, alumina (Al 2 O 3 ), silica, and composite oxides of these materials. Among these, zeolite, montmorillonite, SiO 2 , ZrO 2 , TiO 2 , V 2 O 5 , MgO, alumina (Al 2 O 3 ), silica, and composite oxides of these materials are preferable. A carrier composed of such a material is preferable in that it does not adversely affect the reaction of the reducing agent 4R and is excellent in the carrying capacity of the reducing agent 4R. Here, the carrier does not participate in the reaction of the reducing agent 4R, but merely supports (retains) the reducing agent 4R. As an example of such a form, there is a configuration in which at least a part of the surface of the carrier is coated with the reducing agent 4R.
　還元剤４Ｒに含まれる金属酸化物（酸素キャリア）は、二酸化炭素を還元することができれば、特に限定されないが、第３族～第１２族に属する金属元素から選択される少なくとも１種を含有することが好ましく、第４族～第１２属に属する金属元素から選択される少なくとも１種を含有することがより好ましく、チタニウム、バナジウム、鉄、銅、亜鉛、ニッケル、マンガン、クロミウムおよびセリウム等のうちの少なくとも１種を含有することがさらに好ましく、鉄を含有する金属酸化物または複合酸化物が特に好ましい。これらの金属酸化物は、二酸化炭素の一酸化炭素への変換効率が特に良好なため有用である。 The metal oxide (oxygen carrier) contained in the reducing agent 4R is not particularly limited as long as it can reduce manganese, but contains at least one selected from the metal elements belonging to Group 3 to Group 12. It is preferable, and it is more preferable to contain at least one selected from the metal elements belonging to the 4th to 12th genera, among titanium, vanadium, iron, copper, zinc, nickel, manganese, chromium, cerium and the like. It is more preferable to contain at least one of the above, and a metal oxide or a composite oxide containing iron is particularly preferable. These metal oxides are useful because they have particularly good conversion efficiency of carbon dioxide to carbon monoxide.
　また、各反応器４ａ、４ｂにおいて、還元剤４Ｒ（金属酸化物）自体で管体（円筒状の成形体）４１を作製してもよい。さらに、還元剤４Ｒで、ブロック状、格子状（例えば、網状、ハニカム状）等の成形体を作製し、ハウジング４２内に配置するようにしてもよい。これらの場合、充填剤としての還元剤４Ｒは省略するようにしてもよいし、併用してもよい。
　これらの中では、還元剤４Ｒで網状体を作製し、ハウジング４２内に配置する構成が好ましい。かかる構成の場合、各反応器４ａ、４ｂ内で排ガスおよび還元ガスの通過抵抗が高まるのを防止しつつ、還元剤４Ｒと排ガスおよび還元ガスとの接触の機会を十分に確保することもできる。
　なお、２つの反応器４ａ、４ｂの容積は、互いにほぼ等しく設定され、処理する排ガスの量（炉２０のサイズやガス製造装置１のサイズ）に応じて、適宜設定される。 Further, in each of the reactors 4a and 4b, the tubular body (cylindrical molded body) 41 may be produced by the reducing agent 4R (metal oxide) itself. Further, a block-shaped, lattice-shaped (for example, net-shaped, honeycomb-shaped) molded body may be produced with the reducing agent 4R and arranged in the housing 42. In these cases, the reducing agent 4R as a filler may be omitted or may be used in combination.
Among these, a configuration in which a network body is produced with the reducing agent 4R and arranged in the housing 42 is preferable. In such a configuration, it is possible to sufficiently secure an opportunity for contact between the reducing agent 4R and the exhaust gas and the reducing gas while preventing the passage resistance of the exhaust gas and the reducing gas from increasing in each of the reactors 4a and 4b.
The volumes of the two reactors 4a and 4b are set to be substantially equal to each other, and are appropriately set according to the amount of exhaust gas to be treated (the size of the furnace 20 and the size of the gas production apparatus 1).
　ガスラインＧＬ１の途中には、接続部２側から順に、濃度調整部５と、圧縮部６と、微成分除去部７と、排ガス加熱部（原料ガス加熱部）１０とが設けられている。
　濃度調整部５は、排ガス中に含まれる二酸化炭素の濃度を高める（換言すれば、二酸化炭素を濃縮する）ように調整する。排ガスは、酸素等の不要ガス成分も含む。濃度調整部５で排ガス中に含まれる二酸化炭素の濃度を高めることにより、排ガス中に含まれる不要ガス成分の濃度を相対的に低くすることができる。このため、還元剤４Ｒによる二酸化炭素の一酸化炭素への変換効率に、不要ガス成分が悪影響を及ぼすのを防止または抑制することができる。
　濃度調整部５は、排ガス中に含まれる酸素を除去する酸素除去装置により構成することが好ましい。これにより、ガス製造装置１に持ち込まれる酸素の量を低減すること（すなわち、排ガス中に含まれる酸素の濃度を低くなるように調整すること）ができる。このため、排ガスのガス組成を爆発範囲から乖離させ、排ガスの引火を未然に防止することができる。なお、ガス製造装置１の中でも、酸素除去装置での電気エネルギーの消費が大きいため、後述するような再生可能エネルギーとしての電力を使用することが有効である。 In the middle of the gas line GL1, a concentration adjusting unit 5, a compression unit 6, a fine component removing unit 7, and an exhaust gas heating unit (raw material gas heating unit) 10 are provided in order from the connection unit 2 side.
The concentration adjusting unit 5 adjusts so as to increase the concentration of carbon dioxide contained in the exhaust gas (in other words, to concentrate carbon dioxide). Exhaust gas also contains unnecessary gas components such as oxygen. By increasing the concentration of carbon dioxide contained in the exhaust gas in the concentration adjusting unit 5, the concentration of the unnecessary gas component contained in the exhaust gas can be relatively lowered. Therefore, it is possible to prevent or suppress the adverse effect of the unnecessary gas component on the efficiency of conversion of carbon dioxide to carbon monoxide by the reducing agent 4R.
The concentration adjusting unit 5 is preferably configured by an oxygen removing device that removes oxygen contained in the exhaust gas. As a result, the amount of oxygen brought into the gas production apparatus 1 can be reduced (that is, the concentration of oxygen contained in the exhaust gas can be adjusted to be low). Therefore, the gas composition of the exhaust gas can be deviated from the explosion range, and the ignition of the exhaust gas can be prevented. It should be noted that, among the gas production apparatus 1, since the oxygen removing apparatus consumes a large amount of electric energy, it is effective to use electric power as renewable energy as described later.
　この場合、排ガス中に含まれる酸素の濃度を、排ガス全体に対して１体積％未満に調整することが好ましく、０．５体積％未満に調整することがより好ましく、０．１体積％未満に調整することがさらに好ましい。これにより、排ガスの引火をより確実に防止することができる。
　排ガス中に含まれる酸素を除去する酸素除去装置は、低温分離方式（深冷方式）の分離器、圧力スイング吸着（ＰＳＡ）方式の分離器、膜分離方式の分離器、温度スイング吸着（ＴＳＡ）方式の分離器、化学吸収方式の分離器、化学吸着方式の分離器等のうちの１種または２種以上を用いて構成することができる。
　なお、濃度調整部５では、排ガス中に二酸化炭素を追加することにより、二酸化炭素が高濃度になるように調整してもよい。 In this case, the concentration of oxygen contained in the exhaust gas is preferably adjusted to less than 1% by volume, more preferably less than 0.5% by volume, and less than 0.1% by volume with respect to the entire exhaust gas. It is more preferable to adjust. This makes it possible to more reliably prevent the ignition of the exhaust gas.
Oxygen removal devices that remove oxygen contained in exhaust gas include low temperature separation type (deep cooling type) separators, pressure swing adsorption (PSA) type separators, membrane separation type separators, and temperature swing adsorption (TSA). It can be configured by using one or more of a type separator, a chemical absorption type separator, a chemical adsorption type separator and the like.
The concentration adjusting unit 5 may adjust the concentration of carbon dioxide to a high concentration by adding carbon dioxide to the exhaust gas.
　圧縮部６は、反応器４ａ、４ｂに供給する前の排ガスの圧力を上昇させる。これにより、反応器４ａ、４ｂで一度に処理可能な排ガスの量を増大させることができる。このため、反応器４ａ、４ｂにおける二酸化炭素の一酸化炭素への変換効率をより向上させることができる。
　かかる圧縮部６は、例えば、遠心式圧縮機、軸流式圧縮機のようなターボ圧縮機、往復動圧縮機（レシプロ圧縮機）、ダイアフラム式圧縮機、シングルスクリュー圧縮機、ツインスクリュー圧縮機、スクロール圧縮機、ロータリー圧縮機、ロータリーピストン型圧縮機、スライドベーン型圧縮機のような容積圧縮機、低圧に対応可能なルーツブロワー（二葉送風機）、遠心式のブロワー等で構成することができる。 The compression unit 6 raises the pressure of the exhaust gas before supplying it to the reactors 4a and 4b. This makes it possible to increase the amount of exhaust gas that can be processed at one time by the reactors 4a and 4b. Therefore, the conversion efficiency of carbon dioxide into carbon monoxide in the reactors 4a and 4b can be further improved.
The compression unit 6 includes, for example, a centrifugal compressor, a turbo compressor such as an axial flow compressor, a reciprocating compressor (recipro compressor), a diaphragm compressor, a single screw compressor, a twin screw compressor, and the like. It can be composed of a scroll compressor, a rotary compressor, a rotary piston type compressor, a positive displacement compressor such as a slide vane type compressor, a roots blower (two-leaf blower) capable of supporting low pressure, a centrifugal blower, and the like.
　これらの中でも、圧縮部６は、ガス製造システム１００の大規模化の容易性の観点からは、遠心式圧縮機で構成することが好ましく、ガス製造システム１００の製造コストを低減する観点からは、往復動圧縮機で構成することが好ましい。
　圧縮部６を通過した後の排ガスの圧力は、特に限定されないが、０～１ＭＰａＧであることが好ましく、０～０．５ＭＰａＧであることがより好ましく、０．０１～０．５ＭＰａＧであることがさらに好ましい。この場合、ガス製造装置１の耐圧性を必要以上に高めることなく、反応器４ａ、４ｂにおける二酸化炭素の一酸化炭素への変換効率をさらに向上させることができる。 Among these, the compression unit 6 is preferably configured by a centrifugal compressor from the viewpoint of easiness of increasing the scale of the gas production system 100, and from the viewpoint of reducing the production cost of the gas production system 100, it is preferable. It is preferable to use a reciprocating compressor.
The pressure of the exhaust gas after passing through the compression unit 6 is not particularly limited, but is preferably 0 to 1 MPaG, more preferably 0 to 0.5 MPaG, and preferably 0.01 to 0.5 MPaG. More preferred. In this case, the conversion efficiency of carbon dioxide into carbon monoxide in the reactors 4a and 4b can be further improved without increasing the pressure resistance of the gas production apparatus 1 more than necessary.
　微成分除去部７は、排ガス中に含まれる微成分（微量な不要ガス成分等）を除去する。
　かかる微成分除去部７は、例えば、気液分離器、保護器（ガードリアクター）およびスクラバー（吸収塔）のうちの少なくとも１種の処理器で構成することができる。
　複数の処理器を使用する場合、それらの配置順序は任意であるが、気液分離器と保護器とを組み合わせて使用する場合、気液分離器を保護器より上流側に配置するのが好ましい。この場合、排ガス中からの微成分の除去効率をより高めることができるとともに、保護器の使用期間（寿命）を延長することができる。 The fine component removing unit 7 removes fine components (trace amount of unnecessary gas components, etc.) contained in the exhaust gas.
The fine component removing unit 7 can be composed of, for example, a processor of at least one of a gas-liquid separator, a protector (guard reactor), and a scrubber (absorption tower).
When using a plurality of processors, the order of arrangement thereof is arbitrary, but when using the gas-liquid separator and the protector in combination, it is preferable to arrange the gas-liquid separator on the upstream side of the protector. .. In this case, the efficiency of removing fine components from the exhaust gas can be further improved, and the usage period (life) of the protector can be extended.
　気液分離器は、例えば、圧縮部６で排ガスを圧縮した際に生じる凝縮水（液体）を排ガスから分離する。この場合、凝縮水中には、排ガス中に残存する不要ガス成分等も溶解して除去される。
　気液分離器は、例えば、単なる容器、旋回流式分離器、遠心分離器、表面張力式分離器等で構成することができる。これらの中でも、気液分離器は、構成が単純であり、安価であること等から、単なる容器で構成することが好ましい。この場合、容器内の気液界面には、気体の通過は許容するが、液体の通過を阻止するフィルタを配置するようにしてもよい。
　また、この場合、容器の底部には、液体ラインを接続し、その途中にバルブを設けるようにしてもよい。かかる構成によれば、容器内に貯留された凝縮水は、バルブを開放することにより、液体ラインを介して、ガス製造装置１外に排出することができる。
　なお、液体ラインを後述するタンク３０に接続して、排出する凝縮水を再利用するようにしてもよい。 The gas-liquid separator separates, for example, the condensed water (liquid) generated when the exhaust gas is compressed by the compression unit 6 from the exhaust gas. In this case, unnecessary gas components remaining in the exhaust gas are also dissolved and removed in the condensed water.
The gas-liquid separator can be composed of, for example, a simple container, a swirling flow separator, a centrifuge, a surface tension separator, or the like. Among these, the gas-liquid separator is preferably composed of a simple container because it has a simple structure and is inexpensive. In this case, a filter that allows the passage of gas but blocks the passage of liquid may be arranged at the gas-liquid interface in the container.
Further, in this case, a liquid line may be connected to the bottom of the container and a valve may be provided in the middle thereof. According to such a configuration, the condensed water stored in the container can be discharged to the outside of the gas production apparatus 1 via the liquid line by opening the valve.
The liquid line may be connected to the tank 30, which will be described later, to reuse the discharged condensed water.
　気液分離器で凝縮水が除去された排ガスは、例えば、保護器に供給するように構成することができる。
　かかる保護器は、排ガス中に含まれる微成分であって、還元剤４Ｒとの接触により還元剤４Ｒの活性を低下させる成分（不活化成分）を捕捉可能な物質を備えていることが好ましい。
　かかる構成によれば、排ガスが保護器を通過する際に、保護器内の物質が不活化成分と反応（捕捉）することにより、反応器４ａ、４ｂ内の還元剤４Ｒに到達するのを阻止または抑制して保護すること（すなわち、活性の低下を防止すること）ができる。このため、還元剤４Ｒによる二酸化炭素の一酸化炭素への変換効率が、不活化成分の悪影響により極端に低下するのを防止または抑制することができる。 The exhaust gas from which the condensed water has been removed by the gas-liquid separator can be configured to be supplied to the protector, for example.
It is preferable that the protector is provided with a substance that is a fine component contained in the exhaust gas and can capture a component (inactivating component) that reduces the activity of the reducing agent 4R by contact with the reducing agent 4R.
According to such a configuration, when the exhaust gas passes through the protector, the substance in the protector reacts (captures) with the inactivating component to prevent the exhaust gas from reaching the reducing agent 4R in the reactors 4a and 4b. Alternatively, it can be suppressed and protected (ie, prevent a decrease in activity). Therefore, it is possible to prevent or suppress the efficiency of conversion of carbon dioxide to carbon monoxide by the reducing agent 4R from being extremely lowered due to the adverse effect of the inactivating component.
　かかる物質には、還元剤４Ｒに含まれる組成であって、不活化成分との接触により還元剤４Ｒの活性を低下させる組成を有する物質、具体的には、還元剤４Ｒに含まれる金属酸化物と同一または類似の金属酸化物を使用することができる。ここで、類似の金属酸化物とは、それに含まれる金属元素は同一であるが、組成が異なる金属酸化物、またはそれに含まれる金属元素の種類は異なるが、元素周期律表における族が同一である金属酸化物のことを言う。
　また、不活化成分としては、硫黄、水銀、硫黄化合物、ハロゲン化合物、有機シリコーン、有機リンおよび有機金属化合物から選択される少なくとも１種であることが好ましく、硫黄および硫黄化合物から選択される少なくとも１種であることがより好ましい。かかる不活化成分を予め除去しておけば、還元剤４Ｒの活性が急激に低下するのを効果的に防止することができる。
　なお、上記物質は、還元剤４Ｒの不活化成分と同一の成分により活性が低下する物質であればよく、酸化鉄、酸化亜鉛のような金属酸化物が上記不活化成分の捕捉能に優れる点で好ましい。 Such a substance includes a substance having a composition contained in the reducing agent 4R and having a composition of reducing the activity of the reducing agent 4R by contact with an inactivating component, specifically, a metal oxide contained in the reducing agent 4R. The same or similar metal oxides as can be used. Here, similar metal oxides have the same metal elements contained therein, but have different compositions, or different types of metal elements contained therein, but have the same group in the element periodic table. It refers to a certain metal oxide.
The inactivating component is preferably at least one selected from sulfur, mercury, sulfur compounds, halogen compounds, organic silicones, organic phosphorus and organic metal compounds, and at least one selected from sulfur and sulfur compounds. More preferably, it is a seed. If the inactivating component is removed in advance, it is possible to effectively prevent the activity of the reducing agent 4R from rapidly decreasing.
The substance may be any substance whose activity is reduced by the same component as the inactivating component of the reducing agent 4R, and metal oxides such as iron oxide and zinc oxide are excellent in capturing the inactivating component. Is preferable.
　保護器は、ハウジング内に網材を配置し、上記物質の粒子を網材上に載置する構成、ハウジング内に、上記物質で構成されたハニカム状のフィルタ部材や、円筒状または粒子状の成形体を配置する構成等とすることができる。
　特に、保護器を圧縮部６（気液分離器）と排ガス加熱部１０との間に配置する場合には、上記物質の熱による劣化を防止しつつ、不活化成分の除去効率を向上させることができる。 The protector has a structure in which a mesh material is arranged in a housing and particles of the above substance are placed on the mesh material, a honeycomb-shaped filter member composed of the above-mentioned substance, or a cylindrical or particle-like protector. The structure may be such that the molded body is arranged.
In particular, when the protector is arranged between the compression unit 6 (gas-liquid separator) and the exhaust gas heating unit 10, it is necessary to improve the efficiency of removing inactivated components while preventing deterioration of the above substances due to heat. Can be done.
　排ガス加熱部１０は、反応器４ａ、４ｂに供給する前の排ガスを加熱する。排ガス加熱部１０で反応前（還元前）の排ガスを予め加熱しておくことにより、反応器４ａ、４ｂにおいて、還元剤４Ｒによる二酸化炭素の一酸化炭素への変換（還元）反応をより促進することができる。
　排ガス加熱部１０は、例えば、図３に示すように、電熱器１０１と、熱交換器（エコノマイザ）１０２とで構成することができる。
　熱交換器１０２は、反応器４ａ、４ｂを通過した後のガス（混合ガス）を排出するガスラインＧＬ４（後述参照）を構成する一部の配管を屈曲させ、ガスラインＧＬ１を構成する配管に接近させて構成されている。かかる構成によれば、反応器４ａ、４ｂを通過した後の高温のガス（混合ガス）の熱を利用して、反応器４ａ、４ｂに供給する前の排ガスを熱交換により加熱するため、熱の有効利用を図ることができる。 The exhaust gas heating unit 10 heats the exhaust gas before being supplied to the reactors 4a and 4b. By preheating the exhaust gas before the reaction (before reduction) in the exhaust gas heating unit 10, the conversion (reduction) reaction of carbon dioxide to carbon monoxide by the reducing agent 4R is further promoted in the reactors 4a and 4b. be able to.
The exhaust gas heating unit 10 can be composed of, for example, an electric heater 101 and a heat exchanger (economizer) 102, as shown in FIG.
The heat exchanger 102 bends a part of the pipes constituting the gas line GL4 (see below) for discharging the gas (mixed gas) after passing through the reactors 4a and 4b, and becomes the pipes constituting the gas line GL1. It is configured to be close to each other. According to this configuration, the heat of the high-temperature gas (mixed gas) after passing through the reactors 4a and 4b is used to heat the exhaust gas before being supplied to the reactors 4a and 4b by heat exchange. Can be effectively used.
　かかる熱交換器１０２は、例えば、ジャケット式熱交換器、浸漬コイル式熱交換器、二重管式熱交換器、シェル＆チューブ式熱交換器、プレート式熱交換器、スパイラル式熱交換器等として構成することができる。
　また、排ガス加熱部１０では、電熱器１０１および熱交換器１０２のいずれか一方を省略してもよい。
　排ガス加熱部１０では、電熱器１０１に代えて、燃焼炉等を使用することもできる。ただし、電熱器１０１を使用すれば、その動力源として、再生可能エネルギーとしての電力（電気エネルギー）を使用できるため、環境への負荷を低減することができる。
　再生可能エネルギーとしては、太陽光発電、風カ発電、水力発電、波力発電、潮力発電、バイオマス発電、地熱発電、太陽熱および地中熱から選択される少なくとも１つを利用した電気エネルギーが使用可能である。 The heat exchanger 102 includes, for example, a jacket type heat exchanger, a immersion coil type heat exchanger, a double tube type heat exchanger, a shell & tube type heat exchanger, a plate type heat exchanger, a spiral type heat exchanger, and the like. Can be configured as.
Further, in the exhaust gas heating unit 10, either the electric heater 101 or the heat exchanger 102 may be omitted.
In the exhaust gas heating unit 10, a combustion furnace or the like can be used instead of the electric heater 101. However, if the electric heater 101 is used, electric power (electrical energy) as renewable energy can be used as the power source thereof, so that the load on the environment can be reduced.
As renewable energy, electric energy using at least one selected from solar power generation, wind power generation, hydroelectric power generation, wave power generation, tidal power generation, biomass power generation, geothermal power generation, solar heat and underground heat is used. It is possible.
　また、排ガス加熱部１０の上流側（例えば、微成分除去部７の途中である気液分離器と保護器との間）において、ガスラインＧＬ１から排気ガスラインを分岐させ、その端部にガス製造装置１外に設けられたベント部を接続してもよい。
　この場合、排気ガスラインの途中には、好ましくはバルブが設けられる。
　仮に、ガス製造装置１（ガスラインＧＬ１）内の圧力が必要以上に上昇した場合には、バルブを開放することにより、排気ガスラインを介してベント部から排ガスの一部を排出（放出）することができる。これにより、ガス製造装置１の圧力の上昇による破損を未然に防止することができる。 Further, on the upstream side of the exhaust gas heating unit 10 (for example, between the gas-liquid separator and the protector in the middle of the fine component removing unit 7), the exhaust gas line is branched from the gas line GL1 and the gas is branched at the end thereof. A vent portion provided outside the manufacturing apparatus 1 may be connected.
In this case, a valve is preferably provided in the middle of the exhaust gas line.
If the pressure in the gas production apparatus 1 (gas line GL1) rises more than necessary, a part of the exhaust gas is discharged (released) from the vent portion via the exhaust gas line by opening the valve. be able to. This makes it possible to prevent damage to the gas production apparatus 1 due to an increase in pressure.
　ガスラインＧＬ２は、その一端部において還元ガス供給部３に接続されている。一方、ガスラインＧＬ２は、ガス切換部８および２つのガスラインＧＬ３ａ、ＧＬ３ｂを介して、それぞれ反応部４が備える反応器４ａ、４ｂの入口ポートに接続されている。
　還元ガス供給部３は、二酸化炭素との接触により酸化された還元剤４Ｒを還元する還元物質を含む還元ガスを供給する。本実施形態の還元ガス供給部３は、水の電気分解により水素を発生させる水素発生装置で構成され、この水素発生装置に水を貯留したガス製造装置１外のタンク（還元ガス原料貯留部）３０が接続されている。かかる構成により、水素発生装置（還元ガス供給部３）から供給された水素（還元物質）を含む還元ガスが、ガスラインＧＬ２を通過して、各反応器４ａ、４ｂに供給される。
　水素発生装置によれば、多量の水素を比較的安価かつ簡便に生成することができる。また、ガス製造装置１内で発生する凝縮水を再利用できるという利点もある。なお、ガス製造装置１の中でも、水素発生装置での電気エネルギーの消費が大きいため、上述したような再生可能エネルギーとしての電力を使用することが有効である。 The gas line GL2 is connected to the reducing gas supply unit 3 at one end thereof. On the other hand, the gas line GL2 is connected to the inlet ports of the reactors 4a and 4b provided in the reaction unit 4 via the gas switching unit 8 and the two gas lines GL3a and GL3b, respectively.
The reducing gas supply unit 3 supplies a reducing gas containing a reducing substance that reduces the reducing agent 4R oxidized by contact with carbon dioxide. The reduced gas supply unit 3 of the present embodiment is composed of a hydrogen generator that generates hydrogen by electrolysis of water, and a tank (reduced gas raw material storage unit) outside the gas production apparatus 1 that stores water in this hydrogen generator. 30 is connected. With this configuration, the reducing gas containing hydrogen (reducing substance) supplied from the hydrogen generator (reducing gas supply unit 3) passes through the gas line GL2 and is supplied to the reactors 4a and 4b.
According to the hydrogen generator, a large amount of hydrogen can be generated relatively inexpensively and easily. Further, there is an advantage that the condensed water generated in the gas production apparatus 1 can be reused. Since the hydrogen generator consumes a large amount of electric energy among the gas production apparatus 1, it is effective to use the electric power as the renewable energy as described above.
　なお、水素発生装置には、副生水素を発生する装置を使用することもできる。この場合、副生水素を含む還元ガスが各反応器４ａ、４ｂに供給される。副生水素を発生する装置としては、例えば、塩化ナトリウム水溶液を電気分解する装置、石油を水蒸気改質する装置、アンモニアを製造する装置等が挙げられる。
　また、ガス製造装置１外のコークス炉に接続部を介してガスラインＧＬ２を接続し、コークス炉からの排ガスを還元ガスとして使用するようにしてもよい。この場合、接続部が還元ガス供給部を構成する。コークス炉からの排ガスは、水素およびメタンを主成分とし、水素を５０～６０体積％で含むためである。
　ガスラインＧＬ２の途中には、還元ガス加熱部１１が設けられている。この還元ガス加熱部１１は、反応器４ａ、４ｂに供給する前の還元ガスを加熱する。還元ガス加熱部１１で反応前（酸化前）の還元ガスを予め加熱しておくことにより、反応器４ａ、４ｂにおける還元ガスによる還元剤４Ｒの還元（再生）反応をより促進することができる。 As the hydrogen generator, a device that generates by-product hydrogen can also be used. In this case, the reducing gas containing by-product hydrogen is supplied to each of the reactors 4a and 4b. Examples of the device for generating by-product hydrogen include a device for electrolyzing an aqueous sodium chloride solution, a device for steam reforming petroleum, a device for producing ammonia, and the like.
Further, the gas line GL2 may be connected to the coke oven outside the gas production apparatus 1 via the connecting portion, and the exhaust gas from the coke oven may be used as the reducing gas. In this case, the connecting portion constitutes the reducing gas supply portion. This is because the exhaust gas from the coke oven contains hydrogen and methane as main components and contains hydrogen in an amount of 50 to 60% by volume.
A reducing gas heating unit 11 is provided in the middle of the gas line GL2. The reducing gas heating unit 11 heats the reducing gas before being supplied to the reactors 4a and 4b. By preheating the reducing gas before the reaction (before oxidation) in the reducing gas heating unit 11, the reduction (regeneration) reaction of the reducing agent 4R by the reducing gas in the reactors 4a and 4b can be further promoted.
　還元ガス加熱部１１は、上記排ガス加熱部１０と同様にして構成することができる。還元ガス加熱部１１は、電熱器のみ、熱交換器のみ、電熱器と熱交換器との組み合わせで構成することが好ましく、熱交換器のみ、電熱器と熱交換器との組み合わせで構成することがより好ましい。
　還元ガス加熱部１１が熱交換器を備えれば、反応器４ａ、４ｂを通過した後の高温のガス（例えば、混合ガス）の熱を利用して、反応器４ａ、４ｂに供給する前の還元ガスを熱交換により加熱するため、熱の有効利用を図ることができる。 The reducing gas heating unit 11 can be configured in the same manner as the exhaust gas heating unit 10. The reduction gas heating unit 11 is preferably composed of only an electric heater, only a heat exchanger, and a combination of an electric heater and a heat exchanger, and is composed of only a heat exchanger and a combination of an electric heater and a heat exchanger. Is more preferable.
If the reducing gas heating unit 11 is provided with a heat exchanger, the heat of the high-temperature gas (for example, a mixed gas) after passing through the reactors 4a and 4b is used before being supplied to the reactors 4a and 4b. Since the reducing gas is heated by heat exchange, the heat can be effectively used.
　以上のような構成によれば、ガス切換部８においてガスライン（流路）を切り換えることにより、例えば、酸化前の還元剤４Ｒが収容された反応器４ａに、ガスラインＧＬ３ａを介して排ガスを供給し、酸化後の還元剤４Ｒが収容された反応器４ｂに、ガスラインＧＬ３ｂを介して還元ガスを供給することができる。このとき、反応器４ａでは下記式１の反応が進行し、反応器４ｂでは下記式２の反応が進行する。
　なお、下記式１および式２では、還元剤４Ｒに含まれる金属酸化物が酸化鉄（ＦｅＯｘ－１）である場合を一例として示している。
　　式１：　ＣＯ２　＋　ＦｅＯｘ－１　 →　ＣＯ　＋　ＦｅＯｘ
　　式２：　Ｈ２　＋　ＦｅＯｘ　→　Ｈ２Ｏ　＋　ＦｅＯｘ－１
　その後、ガス切換部８においてガスラインを上記と反対に切り換えることにより、反応器４ａでは上記式２の反応を進行させ、反応器４ｂでは上記式１の反応を進行させることができる。 According to the above configuration, by switching the gas line (flow path) in the gas switching unit 8, for example, the exhaust gas is sent to the reactor 4a containing the reducing agent 4R before oxidation via the gas line GL3a. The reducing gas can be supplied to the reactor 4b in which the reducing agent 4R after oxidation is housed via the gas line GL3b. At this time, the reaction of the following formula 1 proceeds in the reactor 4a, and the reaction of the following formula 2 proceeds in the reactor 4b.
In the following formulas 1 and 2, the case where the metal oxide contained in the reducing agent 4R is iron oxide (FeO x-1 ) is shown as an example.
Equation 1: CO 2 + FeO x-1  → CO + FeO x
Equation 2: H 2 + FeO x → H 2 O + FeO x-1
After that, by switching the gas line in the gas switching unit 8 in the opposite direction to the above, the reaction of the above formula 2 can proceed in the reactor 4a, and the reaction of the above formula 1 can proceed in the reactor 4b.
　なお、上記式１および式２に示す反応は、いずれも吸熱反応である。このため、ガス製造装置１は、還元剤４Ｒに排ガスまたは還元ガスを接触させる際（すなわち、排ガスまたは還元ガスと還元剤４Ｒとの反応の際）に、還元剤４Ｒを加熱する還元剤加熱部（図１中、図示せず。）をさらに有することが好ましい。
　かかる還元剤加熱部を設けることにより、排ガスまたは還元ガスと還元剤４Ｒとの反応における温度を高温に維持して、二酸化炭素の一酸化炭素への変換効率の低下を好適に防止または抑制するとともに、還元ガスによる還元剤４Ｒの再生をさらに促進することができる。 The reactions shown in the above formulas 1 and 2 are endothermic reactions. Therefore, the gas production apparatus 1 is a reducing agent heating unit that heats the reducing agent 4R when the reducing agent 4R is brought into contact with the exhaust gas or the reducing gas (that is, when the exhaust gas or the reducing gas reacts with the reducing agent 4R). It is preferable to further have (not shown in FIG. 1).
By providing such a reducing agent heating unit, the temperature in the reaction between the exhaust gas or the reducing gas and the reducing agent 4R is maintained at a high temperature, and the decrease in the conversion efficiency of carbon dioxide into carbon monoxide is suitably prevented or suppressed. , The regeneration of the reducing agent 4R by the reducing gas can be further promoted.
　ただし、還元剤４Ｒの種類によっては、上記式１および式２に示す反応が発熱反応となる場合がある。この場合、ガス製造装置１は、還元剤加熱部に代えて、還元剤４Ｒを冷却する還元剤冷却部を有することが好ましい。かかる還元剤冷却部を設けることにより、排ガスまたは還元ガスと還元剤４Ｒとの反応の際に、還元剤４Ｒが劣化するのを好適に阻止して、二酸化炭素の一酸化炭素への変換効率の低下を好適に防止または抑制するとともに、還元ガスによる還元剤４Ｒの再生をさらに促進することができる。
　つまり、ガス製造装置１には、還元剤４Ｒの種類（発熱反応または吸熱反応）の違いによって、還元剤４Ｒの温度を調整する還元剤温調部を設けることが好ましい。
　なお、還元剤温調部の好適な構成については、後に詳述する。 However, depending on the type of reducing agent 4R, the reactions represented by the above formulas 1 and 2 may be exothermic reactions. In this case, it is preferable that the gas production apparatus 1 has a reducing agent cooling unit that cools the reducing agent 4R instead of the reducing agent heating unit. By providing such a reducing agent cooling unit, deterioration of the reducing agent 4R is suitably prevented during the reaction between the exhaust gas or the reducing gas and the reducing agent 4R, and the conversion efficiency of carbon dioxide into carbon monoxide is improved. It is possible to suitably prevent or suppress the decrease and further promote the regeneration of the reducing agent 4R by the reducing gas.
That is, it is preferable that the gas production apparatus 1 is provided with a reducing agent temperature control unit that adjusts the temperature of the reducing agent 4R depending on the type of the reducing agent 4R (exothermic reaction or endothermic reaction).
The suitable configuration of the reducing agent temperature control section will be described in detail later.
　反応器４ａ、４ｂの出口ポートには、それぞれ分岐ガスラインＧＬ４ａ、ＧＬ４ｂが接続され、これらがガス合流部Ｊ４において合流して、ガスラインＧＬ４を構成している。また、分岐ガスラインＧＬ４ａ、ＧＬ４ｂの途中には、必要に応じて、それぞれバルブ（図示せず。）が設けられる。
　例えば、バルブの開度を調整することにより、反応器４ａ、４ｂを通過する排ガスおよび還元ガスの通過速度（すなわち、還元剤４Ｒによる排ガスの処理速度および還元ガスによる還元剤４Ｒの処理速度）を設定することができる。
　本実施形態では、反応器４ａ、４ｂおよびガス切換部８により、反応部４が構成されている。 Branch gas lines GL4a and GL4b are connected to the outlet ports of the reactors 4a and 4b, respectively, and these branches at the gas merging portion J4 to form the gas line GL4. Further, valves (not shown) are provided in the middle of the branched gas lines GL4a and GL4b, if necessary.
For example, by adjusting the opening degree of the valve, the passing speed of the exhaust gas and the reducing gas passing through the reactors 4a and 4b (that is, the processing speed of the exhaust gas by the reducing agent 4R and the processing speed of the reducing agent 4R by the reducing gas) can be adjusted. Can be set.
In the present embodiment, the reactor 4 is composed of the reactors 4a and 4b and the gas switching unit 8.
　かかる構成により、反応器４ａ、４ｂのそれぞれを通過したガス（本実施形態では、主に、一酸化炭素および水蒸気）は、ガス合流部Ｊ４において合流することにより混合され、混合ガス（合流ガス）が生成された後、１つのガスラインＧＬ４を通過するようになる。
　このため、ガス切換部８の流路切換状態（バルブの開閉状態）を変更して、反応器４ａ、４ｂのそれぞれで異なる反応を行えば、混合ガスを連続して製造することができ、最終的には、生成ガスも連続して製造することもできる。また、反応器４ａ、４ｂにおいて交互に同一の反応を繰り返し行うため、混合ガス中に含まれる一酸化炭素の濃度を安定化させ、結果として、生成ガス中に含まれる一酸化炭素の濃度を安定化させることもできる。
　したがって、上述したガス製造装置１（ガス製造システム１００）は、二酸化炭素から一酸化炭素を連続かつ安定して製造することができ、工業的に有利である。 With this configuration, the gases (mainly carbon monoxide and steam in this embodiment) that have passed through the reactors 4a and 4b are mixed by merging at the gas merging portion J4, and the mixed gas (merged gas). Will pass through one gas line GL4 after being generated.
Therefore, if the flow path switching state (valve open / closed state) of the gas switching unit 8 is changed and different reactions are performed in the reactors 4a and 4b, the mixed gas can be continuously produced, and finally. The generated gas can also be continuously produced. Further, since the same reaction is alternately repeated in the reactors 4a and 4b, the concentration of carbon monoxide contained in the mixed gas is stabilized, and as a result, the concentration of carbon monoxide contained in the produced gas is stabilized. It can also be turned into.
Therefore, the gas production apparatus 1 (gas production system 100) described above can continuously and stably produce carbon monoxide from carbon dioxide, which is industrially advantageous.
　これに対して、ガス合流部Ｊ４を設けない場合、供給するガスを切り換える際には、ガス切換部８を遮断する（バルブを一旦閉じる）必要が生じ、各反応器４ａ、４ｂをバッチ式とせざるを得ない。このため、一酸化炭素の製造時間が長時間となり、変換効率が悪く、工業的に不利である。
　また、各反応器４ａ、４ｂから排出されるガスの成分が、供給するガスを切り換える度に異なってしまう。このため、各反応器４ａ、４ｂから排出されたガスの後処理工程が複雑になってしまう。
　ここで、混合ガス中に含まれる一酸化炭素の濃度は、通常、特定の範囲（混合ガス全体に対して所定の体積％）に調整するのが好ましい。この濃度が低過ぎると、後述するガス精製部９の性能にもよるが、一酸化炭素を高濃度で含む生成ガスを得るのが難しくなる傾向がある。一方、この濃度の上限値を超えて高くしても、最終的に得られる生成ガス中に含まれる一酸化炭素の濃度をさらに高める効果のそれ以上の増大が期待できない。 On the other hand, when the gas merging section J4 is not provided, it is necessary to shut off the gas switching section 8 (temporarily close the valve) when switching the gas to be supplied, and the reactors 4a and 4b should be batch type. I have no choice but to do so. Therefore, the production time of carbon monoxide becomes long, the conversion efficiency is poor, and it is industrially disadvantageous.
Further, the components of the gas discharged from each of the reactors 4a and 4b are different each time the supplied gas is switched. Therefore, the post-treatment process of the gas discharged from each of the reactors 4a and 4b becomes complicated.
Here, it is usually preferable to adjust the concentration of carbon monoxide contained in the mixed gas to a specific range (a predetermined volume% with respect to the entire mixed gas). If this concentration is too low, it tends to be difficult to obtain a produced gas containing carbon monoxide at a high concentration, although it depends on the performance of the gas purification unit 9 described later. On the other hand, even if the concentration exceeds the upper limit of this concentration, no further increase in the effect of further increasing the concentration of carbon monoxide contained in the finally obtained product gas cannot be expected.
　ガスラインＧＬ４の反応器４ａ、４ｂの反対側の端部には、生成ガスをガス製造装置１外に排出する生成ガス排出部４０が接続されている。
　また、ガスラインＧＬ４の途中には、ガス精製部９が設けられている。
　ガス精製部９では、混合ガスから一酸化炭素を精製して、高濃度の一酸化炭素を含む生成ガスを回収する。なお、混合ガス中の一酸化炭素濃度が十分に高い場合には、ガス精製部９を省略してもよい。
　かかるガス精製部９は、例えば、冷却器、気液分離器、ガス分離器、分離膜およびスクラバー（吸収塔）のうちの少なくとも１種の処理器で構成することができる。
　複数の処理器を使用する場合、それらの配置順序は任意であるが、冷却器と気液分離器とガス分離器とを組み合わせて使用する場合、この順で配置するのが好ましい。この場合、混合ガスからの一酸化炭素の精製効率をより高めることができる。 A generated gas discharging unit 40 for discharging the produced gas to the outside of the gas producing apparatus 1 is connected to the opposite ends of the reactors 4a and 4b of the gas line GL4.
Further, a gas refining unit 9 is provided in the middle of the gas line GL4.
The gas purification unit 9 purifies carbon monoxide from the mixed gas and recovers the produced gas containing a high concentration of carbon monoxide. If the carbon monoxide concentration in the mixed gas is sufficiently high, the gas purification unit 9 may be omitted.
The gas purification unit 9 can be composed of, for example, at least one of a cooler, a gas-liquid separator, a gas separator, a separation membrane, and a scrubber (absorption tower).
When a plurality of processors are used, the order of arrangement thereof is arbitrary, but when a cooler, a gas-liquid separator, and a gas separator are used in combination, it is preferable to arrange them in this order. In this case, the efficiency of purifying carbon monoxide from the mixed gas can be further increased.
　冷却器は、混合ガスを冷却する。これにより、凝縮水（液体）が生成する。
　かかる冷却器は、配管の周囲に冷媒を通過させるためのジャケットを配置したジャケット式の冷却装置、反応器４ａ、４ｂと同様の構成（図２参照）とし、管体内に混合ガスを、管体の周囲に冷媒をそれぞれ通過させる多管式の冷却装置、エアフィンクーラー等を含んで構成することができる。 The cooler cools the mixed gas. As a result, condensed water (liquid) is generated.
Such a cooler has the same configuration as the reactors 4a and 4b, which are jacket-type cooling devices in which a jacket for passing the refrigerant is arranged around the pipe (see FIG. 2), and the mixed gas is introduced into the pipe body. It can be configured to include a multi-tube type cooling device, an air fin cooler, etc., which allow the refrigerant to pass around each of them.
　気液分離器は、冷却器で混合ガスを冷却する際に生じる凝縮水を混合ガスから分離する。このとき、凝縮水には、混合ガス中に残存する不要ガス成分（特に、二酸化炭素）を溶解して除去することができるという利点がある。
　気液分離器は、微成分除去部７の気液分離器と同様に構成することができ、好ましくは単なる容器で構成することができる。この場合、容器内の気液界面には、気体の通過は許容するが、液体の通過を阻止するフィルタを配置するようにしてもよい。
　また、この場合、容器の底部には、液体ラインを接続し、その途中にバルブを設けるようにしてもよい。かかる構成によれば、容器内に貯留された凝縮水は、バルブを開放することにより、液体ラインを介して、ガス製造装置１外に排出（放出）することができる。 The gas-liquid separator separates the condensed water generated when the mixed gas is cooled by the cooler from the mixed gas. At this time, the condensed water has an advantage that unnecessary gas components (particularly carbon dioxide) remaining in the mixed gas can be dissolved and removed.
The gas-liquid separator can be configured in the same manner as the gas-liquid separator of the fine component removing unit 7, and can preferably be configured as a simple container. In this case, a filter that allows the passage of gas but blocks the passage of liquid may be arranged at the gas-liquid interface in the container.
Further, in this case, a liquid line may be connected to the bottom of the container and a valve may be provided in the middle thereof. According to such a configuration, the condensed water stored in the container can be discharged (discharged) to the outside of the gas production apparatus 1 via the liquid line by opening the valve.
　さらに、液体ラインの途中のバルブより下流側には、ドレイントラップを設けることが好ましい。これにより、仮に、バルブが誤作動して、液体ラインに一酸化炭素や水素が流出しても、ドレイントラップに貯留され、ガス製造装置１外に排出されるのを未然に防止することができる。このドレイントラップに代えて、あるいは、ドレイントラップとともに、バルブの誤作動検知機能、バルブが誤作動した際の冗長化対策を施してもよい。
　なお、液体ラインを上述したタンク３０に接続して、排出する凝縮水を再利用するようにしてもよい。 Further, it is preferable to provide a drain trap on the downstream side of the valve in the middle of the liquid line. As a result, even if the valve malfunctions and carbon monoxide or hydrogen flows out to the liquid line, it can be prevented from being stored in the drain trap and discharged to the outside of the gas production apparatus 1. .. Instead of this drain trap, or together with the drain trap, a valve malfunction detection function and a redundancy measure when the valve malfunctions may be provided.
The liquid line may be connected to the tank 30 described above to reuse the discharged condensed water.
　ガス分離器は、例えば、低温分離方式（深冷方式）の分離器、圧力スイング吸着（ＰＳＡ）方式の分離器、膜分離方式の分離器、温度スイング吸着（ＴＳＡ）方式の分離器、金属イオン（例えば、銅イオン）と有機配位子（例えば、５－アジドイソフタル酸）とを複合化した多孔性配位高分子（Ｐｏｒｏｕｓ　Ｃｏｏｒｄｉｎａｔｉｏｎ　Ｐｏｌｙｍｅｒ：ＰＣＰ）を用いた分離器、アミン吸収を利用した分離器等のうちの１種または２種以上を用いて構成することができる。
　また、ガスラインＧＬ４の気液分離器とガス分離器との間には、バルブを設けるようにしてもよい。この場合、バルブの開度を調整することにより、混合ガスの処理速度（生成ガスの製造速度）を調節することができる。 Gas separators include, for example, a low temperature separation type (deep cooling type) separator, a pressure swing adsorption (PSA) type separator, a membrane separation type separator, a temperature swing adsorption (TSA) type separator, and a metal ion. Separator using a porous coordination polymer (PCP) in which (for example, copper ion) and an organic ligand (for example, 5-azidoisophthalic acid) are compounded, separation using amine absorption It can be configured by using one kind or two or more kinds of vessels and the like.
Further, a valve may be provided between the gas-liquid separator of the gas line GL4 and the gas separator. In this case, the processing speed of the mixed gas (production speed of the produced gas) can be adjusted by adjusting the opening degree of the valve.
　本実施形態では、気液分離器から排出される混合ガス中に含まれる一酸化炭素の濃度は、混合ガス全体に対して７５～９０体積％となっている。
　したがって、比較的低い濃度（７５～９０体積％）で一酸化炭素を含む生成ガスを利用可能な分野では、混合ガスから一酸化炭素を精製することなく、そのまま次工程に供給することができる。すなわち、ガス分離器を省略することができる。
　かかる分野としては、例えば、生成ガスから微生物（例えば、クロストリジウム等）による発酵により有価物質（例えば、エタノール等）を合成する分野、生成ガスを燃料または還元剤として使用して鉄鋼を製造する分野、電気デバイスを製造する分野、一酸化炭素を合成原料とする化学品（ホスゲン、酢酸等）を合成する分野等が挙げられる。 In the present embodiment, the concentration of carbon monoxide contained in the mixed gas discharged from the gas-liquid separator is 75 to 90% by volume with respect to the entire mixed gas.
Therefore, in a field where a production gas containing carbon monoxide at a relatively low concentration (75 to 90% by volume) can be used, carbon monoxide can be directly supplied to the next step without being purified from the mixed gas. That is, the gas separator can be omitted.
Such fields include, for example, the field of synthesizing valuable substances (for example, ethanol) by fermentation of the produced gas with a microorganism (for example, clostridium), the field of producing steel using the produced gas as a fuel or a reducing agent, and the like. Examples include the field of manufacturing electric devices and the field of synthesizing chemical products (phosgene, acetic acid, etc.) using carbon monoxide as a synthetic raw material.
　一方、比較的高い濃度（９０体積％超）で一酸化炭素を含む生成ガスを利用する必要がある分野では、混合ガスから一酸化炭素を精製して、高濃度で一酸化炭素を含む生成ガスを得る。
　かかる分野としては、例えば、生成ガスを還元剤として使用する分野（高炉）、生成ガスを燃料として使用して火力により発電する分野、生成ガスを原料として化学品を製造する分野、生成ガスを燃料として使用する燃料電池の分野等が挙げられる。 On the other hand, in the field where it is necessary to utilize the produced gas containing carbon monoxide at a relatively high concentration (more than 90% by volume), the produced gas containing carbon monoxide at a high concentration is obtained by purifying carbon monoxide from the mixed gas. To get.
Such fields include, for example, a field in which the produced gas is used as a reducing agent (blast furnace), a field in which the produced gas is used as a fuel to generate power by thermal power, a field in which a chemical product is produced using the produced gas as a raw material, and a field in which the produced gas is used as a fuel. Examples include the field of fuel cells used as fuel cells.
　次に、ガス製造システム１００の使用方法（作用）について説明する。
　［１］まず、ガス切換部８においてガスライン（流路）を切り換えることにより、接続部２と反応器４ａとを連通し、還元ガス供給部３と反応器４ｂとを連通する。
　［２］次に、この状態で、炉２０から接続部２を介して排ガスの供給を開始する。
　炉２０から供給される排ガスは、通常、５０～３００℃の高温であるが、濃度調整部５に至るまでに、３０～５０℃にまで冷却される。 Next, a method (action) of using the gas production system 100 will be described.
[1] First, by switching the gas line (flow path) in the gas switching unit 8, the connection unit 2 and the reactor 4a are communicated with each other, and the reducing gas supply unit 3 and the reactor 4b are communicated with each other.
[2] Next, in this state, the supply of exhaust gas is started from the furnace 20 via the connection portion 2.
The exhaust gas supplied from the furnace 20 is usually at a high temperature of 50 to 300 ° C., but is cooled to 30 to 50 ° C. by the time it reaches the concentration adjusting unit 5.
　［３］次に、排ガスは、酸素除去装置（濃度調整部５）を通過する。これにより、排ガスから酸素が除去され、排ガス中に含まれる二酸化炭素の濃度が上昇する。
　［４］次に、排ガスは、圧縮部６を通過する。これにより、排ガスの圧力が上昇する。
　［５］次に、排ガスは、微成分除去部７を通過する。これにより、圧縮部６で排ガスを圧縮した際に生じる凝縮水や、還元剤４Ｒの活性を低下させる不活化成分が排ガスから除去される。 [3] Next, the exhaust gas passes through the oxygen removing device (concentration adjusting unit 5). As a result, oxygen is removed from the exhaust gas, and the concentration of carbon dioxide contained in the exhaust gas increases.
[4] Next, the exhaust gas passes through the compression unit 6. As a result, the pressure of the exhaust gas rises.
[5] Next, the exhaust gas passes through the fine component removing unit 7. As a result, the condensed water generated when the exhaust gas is compressed by the compression unit 6 and the inactivating component that reduces the activity of the reducing agent 4R are removed from the exhaust gas.
　［６］次に、排ガスは、排ガス加熱部１０を通過する。これにより、排ガスが加熱される。
　［７］次に、排ガスは、反応器４ａに供給される。反応器４ａでは、還元剤４Ｒにより排ガス中の二酸化炭素が一酸化炭素に還元される。このとき、還元剤４Ｒは、酸化される。
　上記工程［６］における排ガスの加熱温度は、３００～７００℃であることが好ましく、４５０～７００℃であることがより好ましく、６００～７００℃であることがさらに好ましく、６５０～７００℃であることが特に好ましい。排ガスの加熱温度を上記範囲に設定すれば、例えば、二酸化炭素を一酸化炭素へ変換する際の吸熱反応による還元剤４Ｒの急激な温度低下を防止または抑制することができるため、反応器４ａにおける二酸化炭素の還元反応をより円滑に進行させることができる。 [6] Next, the exhaust gas passes through the exhaust gas heating unit 10. This heats the exhaust gas.
[7] Next, the exhaust gas is supplied to the reactor 4a. In the reactor 4a, carbon dioxide in the exhaust gas is reduced to carbon monoxide by the reducing agent 4R. At this time, the reducing agent 4R is oxidized.
The heating temperature of the exhaust gas in the above step [6] is preferably 300 to 700 ° C, more preferably 450 to 700 ° C, further preferably 600 to 700 ° C, and 650 to 700 ° C. Is particularly preferred. If the heating temperature of the exhaust gas is set in the above range, for example, it is possible to prevent or suppress a rapid temperature drop of the reducing agent 4R due to an endothermic reaction when converting carbon dioxide into carbon monoxide. The carbon dioxide reduction reaction can proceed more smoothly.
　［８］上記工程［２］～［７］と並行して、タンク３０から水（還元ガス原料）を水素発生装置（還元ガス供給部３）に供給し、水から水素を生成する。
　［９］次に、水素を含む還元ガスは、還元ガス加熱部１１を通過する。これにより、還元ガスが加熱される。
　［１０］次に、還元ガスは、反応器４ｂに供給される。反応器４ｂでは、還元ガス（水素）により酸化状態の還元剤４Ｒが還元（再生）される。
　上記工程［９］における還元ガスの加熱温度は、３００～７００℃であることが好ましく、４５０～７００℃であることがより好ましく、６００～７００℃であることがさらに好ましく、６５０～７００℃であることが特に好ましい。還元ガスの加熱温度を上記範囲に設定すれば、例えば、酸化状態の還元剤４Ｒを還元（再生）する際の吸熱反応による還元剤４Ｒの急激な温度低下を防止または抑制することができるため、反応器４ｂにおける還元剤４Ｒの還元反応をより円滑に進行させることができる。 [8] In parallel with the above steps [2] to [7], water (reduced gas raw material) is supplied from the tank 30 to the hydrogen generator (reduced gas supply unit 3) to generate hydrogen from the water.
[9] Next, the reducing gas containing hydrogen passes through the reducing gas heating unit 11. As a result, the reducing gas is heated.
[10] Next, the reducing gas is supplied to the reactor 4b. In the reactor 4b, the reducing agent 4R in the oxidized state is reduced (regenerated) by the reducing gas (hydrogen).
The heating temperature of the reducing gas in the above step [9] is preferably 300 to 700 ° C, more preferably 450 to 700 ° C, further preferably 600 to 700 ° C, and 650 to 700 ° C. It is particularly preferable to have. If the heating temperature of the reducing gas is set in the above range, for example, it is possible to prevent or suppress a rapid temperature drop of the reducing agent 4R due to an endothermic reaction when reducing (regenerating) the reducing agent 4R in an oxidized state. The reduction reaction of the reducing agent 4R in the reactor 4b can proceed more smoothly.
　ここで、排ガス加熱部１０による排ガスの加熱温度をＸ［℃］とし、還元ガス加熱部１１による還元ガスの加熱温度をＹ［℃］としたとき、｜Ｘ－Ｙ｜（すなわち、ＸとＹとの差の絶対値）は、０～２５なる関係を満足することが好ましく、０～２０なる関係を満足することがより好ましく、０～１５なる関係を満足することがさらに好ましい。換言すれば、排ガスの加熱温度Ｘと還元ガスの加熱温度Ｙとは同一であっても、若干異なっていてもよい。上記関係を満足するように、ＸおよびＹを設定すれば、二酸化炭素の一酸化炭素への変換と還元ガスによる還元剤４Ｒの還元とを良好なバランスで進行させることができる。
　なお、排ガスの加熱温度Ｘと還元ガスの加熱温度Ｙとを異ならせる場合、還元ガスによる還元剤４Ｒの還元反応に要する熱量が、還元剤４Ｒによる二酸化炭素の還元反応に要する熱量よりも大きくなる傾向にあるため、還元ガスの加熱温度Ｙを排ガスの加熱温度Ｘより高く設定することが好ましい。 Here, when the heating temperature of the exhaust gas by the exhaust gas heating unit 10 is X [° C.] and the heating temperature of the reduced gas by the reducing gas heating unit 11 is Y [° C.], | XY | (that is, X and Y). The absolute value of the difference from 0 to 25) is preferably satisfied with the relationship of 0 to 25, more preferably satisfied with the relationship of 0 to 20, and further preferably satisfied with the relationship of 0 to 15. In other words, the heating temperature X of the exhaust gas and the heating temperature Y of the reducing gas may be the same or slightly different. If X and Y are set so as to satisfy the above relationship, the conversion of carbon dioxide to carbon monoxide and the reduction of the reducing agent 4R by the reducing gas can proceed in a good balance.
When the heating temperature X of the exhaust gas and the heating temperature Y of the reducing gas are different, the amount of heat required for the reduction reaction of the reducing agent 4R by the reducing gas is larger than the amount of heat required for the reduction reaction of carbon dioxide by the reducing agent 4R. Therefore, it is preferable to set the heating temperature Y of the reducing gas higher than the heating temperature X of the exhaust gas.
　本実施形態において、ガス切換部８においてガスラインの切り換えタイミング（すなわち、反応器４ａ、４ｂに供給する排ガスと還元ガスとの切り換えタイミング）は、条件Ｉ：反応器４ａまたは４ｂへ所定の量の排ガスを供給したとき、または条件II：二酸化炭素の一酸化炭素への変換効率が所定の値を下回ったときとすることが好ましい。これにより、二酸化炭素の一酸化炭素への変換効率が大きく低下する前に、反応器４ａ、４ｂの切り換えを行うため、混合ガス中に含まれる一酸化炭素の濃度を増大させ、かつ安定化させることができる。
　なお、条件IIの検出には、反応器４ａ、４ｂの入口および出口ポート付近にそれぞれガス濃度センサを配置しておけばよい。このガス濃度センサの検出値に基づいて、二酸化炭素の一酸化炭素への変換効率を計算により求めることができる。 In the present embodiment, the switching timing of the gas line in the gas switching unit 8 (that is, the switching timing between the exhaust gas supplied to the reactors 4a and 4b and the reducing gas) is the condition I: a predetermined amount to the reactor 4a or 4b. It is preferable that the exhaust gas is supplied or the condition II: the conversion efficiency of carbon dioxide to carbon monoxide falls below a predetermined value. As a result, the reactors 4a and 4b are switched before the efficiency of carbon dioxide conversion to carbon monoxide is significantly reduced, so that the concentration of carbon monoxide contained in the mixed gas is increased and stabilized. be able to.
For the detection of Condition II, gas concentration sensors may be arranged near the inlet and outlet ports of the reactors 4a and 4b, respectively. Based on the detection value of this gas concentration sensor, the conversion efficiency of carbon dioxide to carbon monoxide can be calculated.
　また、混合ガス中に含まれる一酸化炭素の濃度をより安定化させる観点から、反応器４ａ、４ｂへの排ガスの供給量と、反応器４ａ、４ｂへの還元ガスの供給量とは、できる限り近くなるように設定することが好ましい。具体的には、反応器４ａ、４ｂへの排ガスの供給量Ｐ［ｍＬ／分］とし、反応器４ａ、４ｂへの還元ガスの供給量をＱ［ｍＬ／分］としたとき、Ｐ／Ｑは、０．９～２なる関係を満足することが好ましく、０．９５～１．５なる関係を満足することがより好ましい。排ガスの供給量Ｐが多過ぎると、反応器４ａ、４ｂ内の還元剤４Ｒの量によっては、一酸化炭素に変換されることなく、反応器４ａ、４ｂから排出される二酸化炭素の量が増加する傾向がある。 Further, from the viewpoint of further stabilizing the concentration of carbon monoxide contained in the mixed gas, the amount of exhaust gas supplied to the reactors 4a and 4b and the amount of reduced gas supplied to the reactors 4a and 4b can be determined. It is preferable to set it as close as possible. Specifically, when the amount of exhaust gas supplied to the reactors 4a and 4b is P [mL / min] and the amount of reduced gas supplied to the reactors 4a and 4b is Q [mL / min], P / Q. Is preferably satisfied with the relationship of 0.9 to 2, and more preferably satisfied with the relationship of 0.95 to 1.5. If the amount of exhaust gas supplied P is too large, the amount of carbon dioxide emitted from the reactors 4a and 4b increases without being converted to carbon monoxide, depending on the amount of the reducing agent 4R in the reactors 4a and 4b. Tend to do.
　上記条件Ｉにおける所定の量は、還元剤４Ｒに占める質量の割合が最も多い金属元素１モル当たり、二酸化炭素が０．０１～３モルの量であることが好ましく、０．１～２．５モルの量であることがより好ましい。
　また、上記条件IIにおける所定の値は、５０～１００％であることが好ましく、６０～１００％であることがより好ましく、７０～１００％であることがさらに好ましい。なお、所定値の上限は、９５％以下であってもよく、９０％以下であってもよい。
　いずれの場合も、二酸化炭素の一酸化炭素への変換効率が極端に低下する前に、反応器４ａ、４ｂの切り換えが可能であり、結果として、一酸化炭素を高濃度で含む混合ガスを安定して得ることができ、よって、一酸化炭素を高濃度で含む生成ガスを製造することもできる。 The predetermined amount under the above condition I is preferably 0.01 to 3 mol of carbon dioxide per 1 mol of the metal element having the largest proportion of the mass in the reducing agent 4R, and 0.1 to 2.5. More preferably, it is in the amount of moles.
Further, the predetermined value under the above condition II is preferably 50 to 100%, more preferably 60 to 100%, and even more preferably 70 to 100%. The upper limit of the predetermined value may be 95% or less, or 90% or less.
In either case, the reactors 4a and 4b can be switched before the efficiency of carbon dioxide conversion to carbon monoxide drops significantly, and as a result, the mixed gas containing a high concentration of carbon monoxide is stable. Therefore, it is also possible to produce a produced gas containing a high concentration of carbon monoxide.
　なお、還元ガス（還元物質）の供給量Ｑは、還元剤４Ｒに占める質量の割合が最も多い金属元素１モル当たり、水素が０．１～３モルの量であることが好ましく、０．１５～２．５モルの量であることがより好ましい。還元ガスの供給量Ｑを上限値を超えて多くしても、酸化状態の還元剤４Ｒを還元する効果のそれ以上の増大が期待できない。一方、還元ガスの供給量Ｑが少な過ぎると、還元ガス中に含まれる水素の量によっては、還元剤４Ｒの還元が不十分になる場合がある。
　また、反応器４ａ、４ｂに供給する還元ガスの圧力は、大気圧であってもよく、加圧（排ガスと同程度）であってもよい。 The supply amount Q of the reducing gas (reducing substance) is preferably 0.1 to 3 mol, and 0.15 mol, per 1 mol of the metal element having the largest proportion of the mass in the reducing agent 4R. More preferably, the amount is ~ 2.5 mol. Even if the supply amount Q of the reducing gas is increased beyond the upper limit value, no further increase in the effect of reducing the reducing agent 4R in the oxidized state cannot be expected. On the other hand, if the supply amount Q of the reducing gas is too small, the reduction of the reducing agent 4R may be insufficient depending on the amount of hydrogen contained in the reducing gas.
Further, the pressure of the reducing gas supplied to the reactors 4a and 4b may be atmospheric pressure or may be pressurized (similar to the exhaust gas).
　［１１］次に、反応器４ａ、４ｂを通過したガスは、合流して混合ガスが生成される。この時点で、混合ガスの温度は、通常、６００～６５０℃である。この時点での混合ガスの温度が上記範囲であれば、反応器４ａ、４ｂ内の温度が十分に高温に維持されていることを意味し、還元剤４Ｒによる二酸化炭素の一酸化炭素への変換や、還元ガスによる還元剤４Ｒの還元が効率よく進行していると判断することができる。
　［１２］次に、混合ガスは、ガス精製部９に至るまでに、１００～３００℃にまで冷却される。
　［１３］次に、混合ガスは、ガス精製部９を通過する。これにより、例えば、生成された凝縮水および凝縮水に溶解する二酸化炭素等が除去される。その結果、混合ガスから一酸化炭素が精製され、一酸化炭素を高濃度で含む生成ガスが得られる。
　なお、得られる生成ガスの温度は、２０～５０℃である。
　［１４］次に、生成ガスは、生成ガス排出部４０からガス製造装置１外に排出され、次工程に供される。 [11] Next, the gases that have passed through the reactors 4a and 4b merge to form a mixed gas. At this point, the temperature of the mixed gas is usually 600-650 ° C. If the temperature of the mixed gas at this point is in the above range, it means that the temperature in the reactors 4a and 4b is maintained at a sufficiently high temperature, and the conversion of carbon dioxide to carbon monoxide by the reducing agent 4R. Alternatively, it can be determined that the reduction of the reducing agent 4R with the reducing gas is proceeding efficiently.
[12] Next, the mixed gas is cooled to 100 to 300 ° C. by the time it reaches the gas purification unit 9.
[13] Next, the mixed gas passes through the gas refining unit 9. As a result, for example, the generated condensed water and carbon dioxide dissolved in the condensed water are removed. As a result, carbon monoxide is purified from the mixed gas, and a produced gas containing a high concentration of carbon monoxide is obtained.
The temperature of the obtained produced gas is 20 to 50 ° C.
[14] Next, the produced gas is discharged from the generated gas discharging unit 40 to the outside of the gas producing apparatus 1, and is used for the next step.
　＜還元剤加熱部（還元剤温調部）の構成＞
　図４は、還元剤加熱部の構成を示す概略図であり、図５は、還元剤加熱部の他の構成を示す概略図である。
　図４に示す還元剤加熱部１２は、図２に示す多管式の反応器４ａ、４ｂにおいて、複数の管体４１とハウジング４２とで画成される空間４３に供給する媒体と、媒体を空間４３に移送する移送装置１２１と、媒体を加熱する加熱装置１２２とを備えている。 <Structure of reducing agent heating part (reducing agent temperature control part)>
FIG. 4 is a schematic view showing the configuration of the reducing agent heating unit, and FIG. 5 is a schematic diagram showing another configuration of the reducing agent heating unit.
The reducing agent heating unit 12 shown in FIG. 4 has a medium and a medium to be supplied to the space 43 defined by the plurality of tubular bodies 41 and the housing 42 in the multi-tube reactors 4a and 4b shown in FIG. A transfer device 121 for transferring to the space 43 and a heating device 122 for heating the medium are provided.
　本構成例の還元剤加熱部１２は、反応器４ａ、４ｂのそれぞれに接続された循環式の媒体ラインＭＬ１を備え、この媒体ラインＭＬ１に媒体が充填されている。媒体ラインＭＬ１は、途中で分岐した後、各反応器４ａ、４ｂに接続され、その後、再度合流して１つになっている。また、１つになった媒体ラインＭＬ１の途中には、移送装置１２１および加熱装置１２２が配置されている。
　かかる構成によれば、加熱装置１２２で加熱された媒体が、媒体ラインＭＬ１を循環する際に、反応器４ａ、４ｂの空間４３に供給される。これにより、還元剤４Ｒが管体４１を介して間接的に加熱される。また、２つの反応器４ａ、４ｂの還元剤４Ｒの加熱温度をほぼ等しく設定することもできる。
　還元剤４Ｒの加熱温度は、３００～７００℃であることが好ましく、６５０～７００℃であることがより好ましい。加熱温度が高過ぎると、還元剤４Ｒを構成する金属酸化物の種類にもよるが、還元剤４Ｒが劣化して活性が低下し易くなる傾向がある。一方、加熱温度が低過ぎると、高濃度で一酸化炭素を含む生成ガスの製造に要する時間が長くなる傾向がある。 The reducing agent heating unit 12 of this configuration example includes a circulating medium line ML1 connected to each of the reactors 4a and 4b, and the medium line ML1 is filled with a medium. The medium line ML1 is branched in the middle, connected to the reactors 4a and 4b, and then merged again to become one. Further, a transfer device 121 and a heating device 122 are arranged in the middle of the integrated medium line ML1.
According to such a configuration, the medium heated by the heating device 122 is supplied to the space 43 of the reactors 4a and 4b when circulating in the medium line ML1. As a result, the reducing agent 4R is indirectly heated via the tubular body 41. Further, the heating temperatures of the reducing agents 4R of the two reactors 4a and 4b can be set to be substantially equal.
The heating temperature of the reducing agent 4R is preferably 300 to 700 ° C, more preferably 650 to 700 ° C. If the heating temperature is too high, the reducing agent 4R tends to deteriorate and its activity tends to decrease, depending on the type of metal oxide constituting the reducing agent 4R. On the other hand, if the heating temperature is too low, the time required to produce a produced gas containing carbon monoxide at a high concentration tends to be long.
　媒体としては、気体、液体（粘性液体を含む。）等が挙げられる。
　加熱装置１２２は、電熱器のみで構成することができる他、電熱器と排ガス加熱部１０で記載したのと同様の熱交換器とで構成することもできる。
　後者の構成によれば、反応器４ａ、４ｂを通過した後の高温のガスの熱を利用して、反応器４ａ、４ｂに供給する前の媒体を熱交換により加熱するため、熱の有効利用を図ることができる。
　なお、媒体として気体を使用する場合、移送装置１２１は、送風機で構成することができる。また、媒体として液体を使用する場合、移送装置１２１は、ポンプで構成することができる。
　なお、還元剤加熱部１２は、媒体（加熱ガス）を用いる構成に代えて、電気ヒーターで構成することもできる。この場合、電気ヒーターによる加熱は、反応器４ａ、４ｂのハウジング４２に対して行ってよいし、還元剤４Ｒが充填された管体４１に対して別個に行ってもよい。 Examples of the medium include gas, liquid (including viscous liquid) and the like.
The heating device 122 can be composed of only an electric heater, or can also be composed of an electric heater and a heat exchanger similar to that described in the exhaust gas heating unit 10.
According to the latter configuration, the heat of the high-temperature gas after passing through the reactors 4a and 4b is used to heat the medium before being supplied to the reactors 4a and 4b by heat exchange, so that heat can be effectively used. Can be planned.
When a gas is used as the medium, the transfer device 121 can be configured by a blower. Further, when a liquid is used as a medium, the transfer device 121 can be configured by a pump.
The reducing agent heating unit 12 may be configured with an electric heater instead of the configuration using a medium (heating gas). In this case, the heating by the electric heater may be performed on the housing 42 of the reactors 4a and 4b, or may be performed separately on the tube 41 filled with the reducing agent 4R.
　図５に示す還元剤加熱部１２は、非循環式の媒体ラインＭＬ２を備えており、媒体として大気（気体）を使用するように構成されている。
　本構成例では、媒体ラインＭＬ２の大気の供給口側から順に、移送装置１２１（送風機）と、第１熱交換器１２３と、電熱器で構成された加熱装置１２４とが配置され、大気の排出口側に、第２熱交換器１２５が配置されている。
　第１熱交換器１２３および第２熱交換器１２５は、それぞれ熱交換器１０２と同様の構成を有していることが好ましい。
　第１熱交換器１２３は、反応器４ａ、４ｂの管体４１内を通過した後のガス（例えば、混合ガス）と、反応器４ａ、４ｂの空間４３に供給する前の大気との間で熱交換する。一方、第２熱交換器１２５は、反応器４ａ、４ｂの空間４３を通過した後の大気と、反応器４ａ、４ｂに供給する前の排ガスとの間で熱交換する。 The reducing agent heating unit 12 shown in FIG. 5 includes a non-circulating medium line ML2, and is configured to use the atmosphere (gas) as the medium.
In this configuration example, a transfer device 121 (blower), a first heat exchanger 123, and a heating device 124 composed of an electric heater are arranged in order from the air supply port side of the medium line ML2 to exhaust the atmosphere. A second heat exchanger 125 is arranged on the outlet side.
It is preferable that the first heat exchanger 123 and the second heat exchanger 125 each have the same configuration as the heat exchanger 102.
The first heat exchanger 123 is between the gas (for example, a mixed gas) after passing through the tube 41 of the reactors 4a and 4b and the atmosphere before supplying to the space 43 of the reactors 4a and 4b. Heat exchange. On the other hand, the second heat exchanger 125 exchanges heat between the atmosphere after passing through the space 43 of the reactors 4a and 4b and the exhaust gas before supplying to the reactors 4a and 4b.
　反応器４ａ、４ｂを通過した後の高温のガスまたは大気（媒体）の熱を利用して、反応器４ａ、４ｂに供給する前の大気（媒体）または排ガスを熱交換により加熱するため、熱の有効利用を図ることができる。
　なお、第２熱交換器１２５は、反応器４ａ、４ｂに供給する前の排ガスとの間で熱交換する構成に代えて、反応器４ａ、４ｂに供給する前の還元ガスとの間で熱交換する構成としてもよく、反応器４ａ、４ｂに供給する前の排ガスおよび還元ガスの双方との間で熱交換する構成としてもよい。
　また、図５に示す構成例によれば、図４に示す構成例より、移送装置１２１に接触する媒体の温度が低くなるため、比較的安価な耐熱性の低い移送装置でも使用可能であるという利点がある。 Heat is used to heat the atmosphere (medium) or exhaust gas before being supplied to the reactors 4a and 4b by heat exchange using the heat of the high-temperature gas or atmosphere (medium) after passing through the reactors 4a and 4b. Can be effectively used.
The second heat exchanger 125 replaces the configuration of exchanging heat with the exhaust gas before being supplied to the reactors 4a and 4b, and heat is exchanged with the reducing gas before being supplied to the reactors 4a and 4b. It may be configured to be exchanged, or it may be configured to exchange heat with both the exhaust gas and the reducing gas before being supplied to the reactors 4a and 4b.
Further, according to the configuration example shown in FIG. 5, since the temperature of the medium in contact with the transfer device 121 is lower than that of the configuration example shown in FIG. 4, it is possible to use a relatively inexpensive transfer device having low heat resistance. There are advantages.
　ここで、反応器４ａ、４ｂ（還元剤４Ｒ）を加熱するのに燃焼炉等を用いると、還元剤４Ｒの加熱温度（反応温度）を維持するのに、燃料を燃焼する必要が生じる。このため、二酸化炭素が発生し、二酸化炭素を大気中に放出せざるを得ないことになる。
　これに対して、還元剤加熱部１２を図４および図５に示す構成とすることにより、移送装置１２１および加熱装置１２２、１２４の動力源として、上述したような再生可能エネルギーとしての電力（電気エネルギー）を使用できるため、環境への負荷を低減することができる。
　また、ガス製造装置１内に存在する可燃ガスへの引火の可能性をより確実に低減することができるという利点もある。 Here, if a combustion furnace or the like is used to heat the reactors 4a and 4b (reducing agent 4R), it becomes necessary to burn the fuel in order to maintain the heating temperature (reaction temperature) of the reducing agent 4R. For this reason, carbon dioxide is generated, and carbon dioxide has to be released into the atmosphere.
On the other hand, by configuring the reducing agent heating unit 12 as shown in FIGS. 4 and 5, electric power (electricity) as renewable energy as described above can be used as a power source for the transfer device 121 and the heating devices 122 and 124. Since energy) can be used, the burden on the environment can be reduced.
Further, there is an advantage that the possibility of ignition of the combustible gas existing in the gas production apparatus 1 can be more reliably reduced.
　なお、還元剤加熱部は、図４および図５に示す構成に代えて、還元剤４Ｒに対してマイクロ波を照射する照射装置を備える構成とすることもできる。
　マイクロ波の照射により還元剤４Ｒを加熱する構成によれば、還元剤４Ｒを比較的短時間で、目的の温度まで加熱することができる。また、還元剤４Ｒの表面付近のみならず、中心部まで均一に加熱し易い。さらに、還元剤４Ｒの加熱温度を精密に制御し易い。よって、照射装置を使用すれば、生成ガスの製造効率をより高めることができる。加えて、かかる照射装置は、図４および図５に示す構成と比較して、小型化が可能である。
　また、マイクロ波の照射の場合、還元剤４Ｒの表面付近のみを局所的（優先的）に目的とする温度に上昇させることができる。このため、高温で反応が進行する場合（吸熱反応の場合）には、その効率を高め易い。この場合、還元剤４Ｒの表面付近のみの温度を上昇させるだけのエネルギーを投入すればよいので、エネルギー効率も向上する。 In addition, instead of the configuration shown in FIGS. 4 and 5, the reducing agent heating unit may be configured to include an irradiation device that irradiates the reducing agent 4R with microwaves.
According to the configuration in which the reducing agent 4R is heated by irradiation with microwaves, the reducing agent 4R can be heated to a target temperature in a relatively short time. Further, it is easy to uniformly heat not only the vicinity of the surface of the reducing agent 4R but also the central portion. Further, it is easy to precisely control the heating temperature of the reducing agent 4R. Therefore, if an irradiation device is used, the production efficiency of the generated gas can be further improved. In addition, the irradiation device can be miniaturized as compared with the configurations shown in FIGS. 4 and 5.
Further, in the case of microwave irradiation, only the vicinity of the surface of the reducing agent 4R can be locally (prioritically) raised to the target temperature. Therefore, when the reaction proceeds at a high temperature (in the case of an endothermic reaction), it is easy to increase the efficiency. In this case, since it is sufficient to input enough energy to raise the temperature only near the surface of the reducing agent 4R, the energy efficiency is also improved.
　マイクロ波は、周波数３００ＭＨｚ～３００ＧＨｚの電磁波を意味し、周波数３００～３０００ＭＨｚの極超短波（ＵＨＦ）、周波数３～３０ＧＨｚのセンチメートル波（ＳＨＦ）、周波数３０～３００ＧＨｚのミリ波（ＥＨＦ）、周波数３００～３０００ＧＨｚのサブミリ波（ＳＨＦ）に分類される。中でも、マイクロ波としては、極超短波（ＵＨＦ）が好ましい。極超短波（ＵＨＦ）を使用することにより、還元剤４Ｒをより短時間で、目的の温度まで加熱することができる。
　なお、マイクロ波の照射を行う場合、電波法に準拠した電波の漏洩対策が適切に講じられる。 Microwave means an electromagnetic wave having a frequency of 300 MHz to 300 GHz, an ultra-high frequency wave (UHF) having a frequency of 300 to 3000 MHz, a centimeter wave (SHF) having a frequency of 3 to 30 GHz, a millimeter wave (EHF) having a frequency of 30 to 300 GHz, and a frequency 300. It is classified as a submillimeter wave (SHF) of ~ 3000 GHz. Among them, ultra high frequency (UHF) is preferable as the microwave. By using ultra high frequency (UHF), the reducing agent 4R can be heated to a target temperature in a shorter time.
When irradiating microwaves, measures against radio wave leakage in accordance with the Radio Law are taken appropriately.
　また、マイクロ波の照射は、連続的に行ってもよく、間欠的（パルス的）に行ってもよい。
　マイクロ波の照射を連続的に行えば、二酸化炭素の一酸化炭素への変換効率および還元ガスによる還元剤４Ｒの再生（還元）効率がさらに高まることを、本発明者らは知見している。その理由は、必ずしも明確ではないが、反応器４ａ、４ｂ内に供給される排ガス中に含まれる二酸化炭素、還元ガス中に含まれる水素および還元剤４Ｒが、連続的に照射されるマイクロ波により活性化されることが要因であると考えられる。
　一方、マイクロ波の照射を間欠的に行う場合には、二酸化炭素の一酸化炭素への変換および還元ガスによる還元剤４Ｒの再生（還元）の際の吸熱反応に必要なエネルギー分だけを補償するように、所定のタイミングでマイクロ波を照射すればよいので、エネルギー効率を高めることができる。 Further, the microwave irradiation may be performed continuously or intermittently (pulse-like).
The present inventors have found that continuous irradiation with microwaves further enhances the conversion efficiency of carbon dioxide into carbon monoxide and the regeneration (reduction) efficiency of the reducing agent 4R by the reducing gas. The reason is not always clear, but carbon dioxide contained in the exhaust gas supplied into the reactors 4a and 4b, hydrogen contained in the reducing gas and the reducing agent 4R are continuously irradiated with microwaves. It is thought that activation is a factor.
On the other hand, when microwave irradiation is performed intermittently, only the energy required for the endothermic reaction during the conversion of carbon dioxide to carbon monoxide and the regeneration (reduction) of the reducing agent 4R with the reducing gas is compensated. As described above, it is sufficient to irradiate the microwave at a predetermined timing, so that the energy efficiency can be improved.
　マイクロ波の照射による加熱の場合、排ガスの加熱温度、還元ガスの加熱温度及び還元剤４Ｒの加熱温度は、それぞれ上述と同じ範囲としてもよく、上述と異なる範囲としてもよい。例えば、上記各加熱温度は、３００～７００℃に設定することができる。
　なお、照射装置は、反応器４ａ、４ｂの内部に配置してもよく、外部に配置してもよい。上述したように、濃度調整部５により、排ガスのガス組成を爆発範囲から乖離させておけば、マイクロ波の照射条件によらず、排ガスに対する着火源となることを好適に防止することができる。
　また、照射装置の動力源には、電気エネルギーが使用されるため、この電気エネルギーを再生可能エネルギーに切り換え易いというメリットもある。 In the case of heating by microwave irradiation, the heating temperature of the exhaust gas, the heating temperature of the reducing gas, and the heating temperature of the reducing agent 4R may be in the same range as described above, or may be different from the above range. For example, each of the above heating temperatures can be set to 300 to 700 ° C.
The irradiation device may be arranged inside the reactors 4a and 4b, or may be arranged outside. As described above, if the gas composition of the exhaust gas is deviated from the explosion range by the concentration adjusting unit 5, it is possible to suitably prevent the exhaust gas from becoming an ignition source regardless of the microwave irradiation conditions. ..
Further, since electric energy is used as the power source of the irradiation device, there is an advantage that this electric energy can be easily switched to renewable energy.
　上述したように、還元剤４Ｒによる反応が発熱反応である場合、還元剤温調部を還元剤冷却部として構成することができる。この場合、例えば、図４および図５に示す構成において、第１熱交換器１２３および第２熱交換器１２５を省略し、加熱装置１２２、１２４を冷却装置に変更すればよい。冷却装置としては、ジャケット式の冷却装置、多管式の冷却装置等が挙げられる。この場合も、還元剤４Ｒの冷却温度（温調後の温度）を、上述と同じ範囲とするのが好ましい。 As described above, when the reaction by the reducing agent 4R is an exothermic reaction, the reducing agent temperature control unit can be configured as the reducing agent cooling unit. In this case, for example, in the configurations shown in FIGS. 4 and 5, the first heat exchanger 123 and the second heat exchanger 125 may be omitted, and the heating devices 122 and 124 may be replaced with cooling devices. Examples of the cooling device include a jacket type cooling device, a multi-tube type cooling device, and the like. Also in this case, it is preferable that the cooling temperature (temperature after temperature adjustment) of the reducing agent 4R is in the same range as described above.
　＜接続部付近の構成＞
　図６は、本発明のガス製造装置と炉との接続部（原料ガス供給部）付近の構成を示す概略図である。
　図６に示すように、炉２０は、排ガスを大気に排出する煙突２１を備えている。煙突２１の高さ方向の途中には、分岐部２２にガスライン２３の一端部が接続されている。また、このガスライン２３の他端部は、ガス製造装置１の接続部２に接続されている。 <Configuration near the connection>
FIG. 6 is a schematic view showing a configuration in the vicinity of a connection portion (raw material gas supply portion) between the gas production apparatus of the present invention and the furnace.
As shown in FIG. 6, the furnace 20 includes a chimney 21 that discharges exhaust gas to the atmosphere. One end of the gas line 23 is connected to the branch portion 22 in the middle of the chimney 21 in the height direction. Further, the other end of the gas line 23 is connected to the connection portion 2 of the gas production apparatus 1.
　図６に示す構成では、接続部２と濃度調整部５との間に、冷却部１３が設けられている。そして、この冷却部１３は、冷却装置１３１と、冷却装置１３１に接続された容器１３２とを備えている。冷却装置１３１は、上述したようなジャケット式の冷却装置、多管式の冷却装置等で構成することができる。
　炉２０から供給される排ガスは、水蒸気の他、酸化ガス成分（ＳＯｘ、ＨＣｌ等）も含むため、冷却部１３での冷却により、酸化ガス成分とともに、水蒸気を凝縮させ、酸化ガス成分が溶解した凝縮水（酸性水溶液）として除去することが好ましい。これにより、ガスラインＧＬ１を構成する配管の腐食を好適に防止することができる。
　本構成例では、冷却装置１３１で排ガスを冷却することにより酸性水溶液が生成され、この酸性水溶液は、容器１３２に貯留され、排ガスと分離される。また、容器１３２内の気液界面には、気体の通過は許容するが、液体の通過を阻止するフィルタを配置するようにしてもよい。
　かかる構成の場合、分岐部２２と冷却装置１３１との離間距離（図６中、Ｌ１）は、特に限定されないが、１０ｍ以下が好ましく、１～５ｍであることがより好ましい。離間距離Ｌ１を上記範囲に設定すれば、ガスラインＧＬ１の目的としない箇所において、酸性ガスが溶解した凝縮水（酸性水溶液）が生成されるのを阻止して、ガスラインＧＬ１を構成する配管の腐食をより確実に防止することができる。 In the configuration shown in FIG. 6, a cooling unit 13 is provided between the connection unit 2 and the concentration adjusting unit 5. The cooling unit 13 includes a cooling device 131 and a container 132 connected to the cooling device 131. The cooling device 131 can be configured by a jacket type cooling device, a multi-tube type cooling device, or the like as described above.
Since the exhaust gas supplied from the furnace 20 contains not only water vapor but also an oxidation gas component (SO x , HCl, etc.), the water vapor is condensed together with the oxidation gas component by cooling in the cooling unit 13, and the oxidation gas component is dissolved. It is preferable to remove it as condensed water (acidic aqueous solution). This makes it possible to suitably prevent corrosion of the pipes constituting the gas line GL1.
In this configuration example, an acidic aqueous solution is generated by cooling the exhaust gas with the cooling device 131, and the acidic aqueous solution is stored in the container 132 and separated from the exhaust gas. Further, a filter that allows the passage of gas but blocks the passage of liquid may be arranged at the gas-liquid interface in the container 132.
In the case of such a configuration, the separation distance (L1 in FIG. 6) between the branch portion 22 and the cooling device 131 is not particularly limited, but is preferably 10 m or less, and more preferably 1 to 5 m. If the separation distance L1 is set within the above range, it is possible to prevent the generation of condensed water (acidic aqueous solution) in which acid gas is dissolved at a place not intended for the gas line GL1 and to prevent the generation of condensed water (acidic aqueous solution) in the gas line GL1. Corrosion can be prevented more reliably.
　また、ガス製造システム１００が例えば寒冷地等に施設される場合、特に、炉２０とガス製造装置１との離間距離Ｌ２によっては、ガスライン２３の途中で凝縮水が生成され、さらに凍結に至ることがある。これが原因で、ガスライン２３を構成する配管が破損するおそれがある。
　したがって、このようなトラブルを防ぐために、ガスライン２３中の排ガスを加熱することが好ましい。加熱温度は、凍結が生じない温度であればよいが、酸露点温度（例えば、１２０℃）以上であることが好ましく、１２０～１５０℃であることがより好ましい。これにより、ガスライン２３を構成する配管が破損するのを防止しつつ、酸性ガスが溶解した凝縮水の生成による配管の腐食も好適に防止することができる。
　なお、ガスライン２３中の排ガスを加熱するには、例えば、ガスライン２３を構成する配管の周囲に電熱線（ヒータ）を巻回して配置すればよい。また、耐腐食目的の場合、ヒーターを用いず、耐腐食性の樹脂材料（例えば、フッ素系樹脂材料）で構成される樹脂ライニング配管等を用いてもよい。
　なお、本構成例においては、必要に応じて、容器１３２を省略してもよい。 Further, when the gas production system 100 is installed in a cold region, for example, condensed water is generated in the middle of the gas line 23 depending on the separation distance L2 between the furnace 20 and the gas production apparatus 1, which leads to further freezing. Sometimes. This may damage the piping that constitutes the gas line 23.
Therefore, in order to prevent such troubles, it is preferable to heat the exhaust gas in the gas line 23. The heating temperature may be any temperature at which freezing does not occur, but is preferably an acid dew point temperature (for example, 120 ° C.) or higher, and more preferably 120 to 150 ° C. As a result, it is possible to prevent the pipes constituting the gas line 23 from being damaged, and to suitably prevent corrosion of the pipes due to the generation of condensed water in which acid gas is dissolved.
In order to heat the exhaust gas in the gas line 23, for example, a heating wire (heater) may be wound around the piping constituting the gas line 23 and arranged. Further, for the purpose of corrosion resistance, a resin lining pipe or the like made of a corrosion resistant resin material (for example, a fluorine-based resin material) may be used without using a heater.
In this configuration example, the container 132 may be omitted if necessary.
　なお、上記実施形態では、原料ガスの一例として排ガスを代表に説明したが、上述したように、原料ガスとしては、二酸化炭素を含むガスであれば、特に排ガスに限定されるものではない。したがって、上記実施形態において、排ガスの各種処理条件（圧縮部６による加圧の圧力、反応器４ａ、４ｂへ供給する前の加熱温度、反応器４ａ、４ｂへの供給量等を含む。）は、その他の原料ガスについても同様に適用することができる。 In the above embodiment, exhaust gas has been described as an example of the raw material gas, but as described above, the raw material gas is not particularly limited to the exhaust gas as long as it contains carbon dioxide. Therefore, in the above embodiment, various treatment conditions of the exhaust gas (including the pressure of pressurization by the compression unit 6, the heating temperature before supplying to the reactors 4a and 4b, the amount of supply to the reactors 4a and 4b, and the like). , And other raw material gases can be applied in the same manner.
　以上のようなガス製造装置１、ガス製造システム１００を使用して、二酸化炭素を含む原料ガスから、一酸化炭素を含む生成ガスを製造することができる。
　＜ガス製造方法＞
　本実施形態のガス製造方法は、上記排ガス（原料ガス）と、上記還元剤４Ｒとを接触させて、一酸化炭素を含む生成ガスを製造する方法であり、Ｉ：還元剤４Ｒを内部に配置した複数の反応器４ａ、４ｂと、排ガスと、二酸化炭素との接触により酸化された還元剤４Ｒを還元する水素（還元物質）を含む還元ガスとを準備し、II：排ガスと還元ガスとを供給する反応器４ａ、４ｂを切り換えることにより、各反応器４ａ、４ｂ内において還元剤４Ｒに排ガスと還元ガスとを交互に接触させて、二酸化炭素を一酸化炭素に変換した後、酸化された還元剤４Ｒを還元し、III：反応器４ａ、４ｂを通過した後のガス同士を合流させて、混合ガスを生成し、IV：混合ガスをそのまま、または、混合ガスから一酸化炭素を精製することにより、生成ガスとして回収するのに際して、反応器４ａ、４ｂへ所定の量の排ガスを供給したとき、または、二酸化炭素の一酸化炭素への変換効率が所定の値を下回ったとき、各反応器４ａ、４ｂに供給する排ガスと還元ガスとを切り換える。 Using the gas production apparatus 1 and the gas production system 100 as described above, a production gas containing carbon monoxide can be produced from a raw material gas containing carbon dioxide.
<Gas production method>
The gas production method of the present embodiment is a method of producing a produced gas containing carbon monoxide by contacting the exhaust gas (raw material gas) with the reducing agent 4R, and I: reducing agent 4R is arranged inside. Prepare a plurality of reactors 4a and 4b, a reducing gas containing hydrogen (reducing substance) that reduces the reducing agent 4R oxidized by contact with the exhaust gas and carbon dioxide, and II: exhaust gas and reducing gas. By switching the reactors 4a and 4b to be supplied, the exhaust gas and the reducing gas were alternately brought into contact with the reducing agent 4R in each of the reactors 4a and 4b to convert carbon dioxide into carbon monoxide and then oxidized. The reducing agent 4R is reduced, and III: the gases after passing through the reactors 4a and 4b are merged to generate a mixed gas, and IV: the mixed gas is used as it is, or carbon monoxide is purified from the mixed gas. Therefore, when recovering as a produced gas, when a predetermined amount of exhaust gas is supplied to the reactors 4a and 4b, or when the conversion efficiency of carbon dioxide to carbon monoxide falls below a predetermined value, each reaction The exhaust gas supplied to the vessels 4a and 4b and the reducing gas are switched.
　＜製造物＞
　上記ガス製造装置１、ガス製造システム１００を使用して製造された生成ガスは、通常、一酸化炭素の濃度が６０体積％以上、好ましくは７５体積％以上、より好ましくは９０体積％以上である。
　また、上述したような生成ガスは、微生物（例えば、クロストリジウム等）による発酵により有価物質（例えば、エタノール等）を合成する分野、燃料または還元剤として使用して鉄鋼を製造する分野、電気デバイスを製造する分野、一酸化炭素を合成原料とする化学品（ホスゲン、酢酸等）を製造する分野、還元剤として使用する分野（高炉）、燃料として使用して火力により発電する分野、燃料として使用する燃料電池の分野等において使用することができる。 <Manufacturing>
The produced gas produced by using the gas production apparatus 1 and the gas production system 100 usually has a carbon monoxide concentration of 60% by volume or more, preferably 75% by volume or more, and more preferably 90% by volume or more. ..
In addition, the generated gas as described above can be used in fields where valuable substances (eg, ethanol, etc.) are synthesized by fermentation with microorganisms (eg, clostridium, etc.), fields in which steel is produced by using it as a fuel or reducing agent, and electrical devices. Fields to manufacture, fields to manufacture chemicals (phosgen, acetic acid, etc.) using carbon monoxide as a synthetic raw material, fields to use as a reducing agent (blast furnace), fields to use as fuel to generate electricity by thermal power, use as fuel It can be used in the field of fuel cells and the like.
　また、上述したガス製造システム１００（ガス製造装置１）において、反応器４ａ、４ｂを通過したガスは、反応器４ａ、４ｂを通過した直後に合流する構成であったが、合流する前に各種処理が施されてもよい。すなわち、分岐ガスラインＧＬ４ａ、ＧＬ４ｂの途中には、任意の目的で、少なくとも１種の処理器を設けることができる。
　次に、かかる構成のガス製造システム１００について説明する。
　図７は、本発明のガス製造システムの他の実施形態を示す概略図であり、図８は、図７の精製器の構成を模式的に示す断面図である。
　以下、図７に示すガス製造システム１００について、図１に示すガス製造システム１００との相違点を中心に説明し、同様の事項については、その説明を省略する。
　図７に示すガス製造システム１００は、さらに、分岐ガスラインＧＬ４ａ、ＧＬ４ｂの途中に設けられた精製器１４ａ、１４ｂを有している。すなわち、各精製器１４ａ、１４ｂは、対応する反応器４ａ、４ｂの下流側に接続され、反応器４ａ、４ｂ及び精製器１４ａ、１４ｂを順次通過したガスは、ガス合流部Ｊ４において合流する。 Further, in the gas production system 100 (gas production apparatus 1) described above, the gases that have passed through the reactors 4a and 4b are configured to merge immediately after passing through the reactors 4a and 4b, but various types are used before they merge. The treatment may be applied. That is, at least one kind of processor can be provided in the middle of the branched gas lines GL4a and GL4b for any purpose.
Next, the gas production system 100 having such a configuration will be described.
FIG. 7 is a schematic view showing another embodiment of the gas production system of the present invention, and FIG. 8 is a cross-sectional view schematically showing the configuration of the purifier of FIG. 7.
Hereinafter, the gas production system 100 shown in FIG. 7 will be described mainly on the differences from the gas production system 100 shown in FIG. 1, and the same matters will be omitted.
The gas production system 100 shown in FIG. 7 further has refiners 14a and 14b provided in the middle of the branched gas lines GL4a and GL4b. That is, each of the purifiers 14a and 14b is connected to the downstream side of the corresponding reactors 4a and 4b, and the gas passing through the reactors 4a and 4b and the purifiers 14a and 14b sequentially merges at the gas confluence portion J4.
　各精製器１４ａ、１４ｂは、図８に示すように、複数の分離筒１４１と、複数の分離筒１４１を収納したハウジング（精製器本体）１４２とを備える多管式の精製装置で構成されている。かかる多管式の精製装置によれば、反応器４ａ、４ｂを通過したガスと分離筒１４１との接触の機会を十分に確保することができる。
　各精製器１４ａ、１４ｂは、還元剤４Ｒとの接触により生成した水（還元物質の酸化物）と水素（還元物質）との分離、および、一酸化炭素と二酸化炭素との分離のうちの少なくとも一方が可能に構成されていることが好ましい。特に、分離筒１４１は、その壁部を水（水蒸気）または一酸化炭素を透過させ、水素または二酸化炭素と分離するように構成されることが好ましい。 As shown in FIG. 8, each of the refiners 14a and 14b is composed of a multi-tube refining device including a plurality of separation cylinders 141 and a housing (refiner main body) 142 accommodating the plurality of separation cylinders 141. There is. According to such a multi-tube purification apparatus, it is possible to sufficiently secure an opportunity for contact between the gas passing through the reactors 4a and 4b and the separation cylinder 141.
Each of the purifiers 14a and 14b has at least one of the separation of water (oxide of the reducing substance) and hydrogen (reducing substance) generated by contact with the reducing agent 4R and the separation of carbon monoxide and carbon dioxide. It is preferable that one is configured to be possible. In particular, it is preferable that the separation cylinder 141 is configured so that its wall portion allows water (water vapor) or carbon monoxide to permeate and separates from hydrogen or carbon dioxide.
　本実施形態では、分離筒１４１を透過した水および一酸化炭素は、精製器１４ａ、１４ｂから分岐ガスラインＧＬ４ａ、ＧＬ４ｂに排出される。一方、分離筒１４１内を通過した還元ガス（未反応の水素）および排ガス（未反応の二酸化炭素）は、ハウジング１４２（空間１４３）に接続されたガスラインＧＬ１４ａ、ＧＬ１４ｂに排出される。
　これらのガスラインＧＬ１４ａ、ＧＬ１４ｂは、それぞれガスラインＧＬ１およびガスラインＧＬ２の途中に接続されてもよい。これにより、未反応の水素および二酸化炭素を再利用することができる。
　分岐ガスラインＧＬ４ａ、ＧＬ４ｂに排出されるガスには、水または一酸化炭素以外の他のガス成分が含まれていてもよいし、ガスラインＧＬ１４ａ、ＧＬ１４ｂに排出されるガスにも、水素または二酸化炭素以外の他のガス成分が含まれていてもよい。 In the present embodiment, the water and carbon monoxide that have passed through the separation cylinder 141 are discharged from the refiners 14a and 14b to the branched gas lines GL4a and GL4b. On the other hand, the reducing gas (unreacted hydrogen) and the exhaust gas (unreacted carbon dioxide) that have passed through the separation cylinder 141 are discharged to the gas lines GL14a and GL14b connected to the housing 142 (space 143).
These gas lines GL14a and GL14b may be connected in the middle of the gas line GL1 and the gas line GL2, respectively. This allows unreacted hydrogen and carbon dioxide to be reused.
The gas discharged to the branched gas lines GL4a and GL4b may contain gas components other than water or carbon monoxide, and the gas discharged to the gas lines GL14a and GL14b may also contain hydrogen or carbon dioxide. It may contain gas components other than carbon.
　なお、一酸化炭素と二酸化炭素との分離、および、水と水素との分離は、それぞれ、凝縮（液化）する温度の違いを利用して、各反応器４ａ、４ｂから排出されるガスを冷却することによっても可能である。しかしながら、この場合、反応器４ａ、４ｂの下流側で、分離後のガス成分を高温状態で使用する際（例えば、上記熱交換器１０２で使用する際等）には、再度、加熱する必要があり、熱エネルギーに無駄が生じる。これに対して、精製器１４ａ、１４ｂによれば、高温（例えば、２００～５００℃）でガス成分の分離操作を行うことができるので、分離後のガス成分の温度の低下が生じ難いため、生成ガスの製造全体における熱エネルギーの削減に寄与することができる。
　なお、精製器１４ａ、１４ｂによる分離後のガス成分の温度の低下をより確実に防止する観点からは、分離筒１４１を加熱する加熱装置（例えば、上記マイクロ波を照射する照射装置等）を設けるようにしてもよい。 The separation of carbon monoxide and carbon dioxide and the separation of water and hydrogen cool the gas discharged from each reactor 4a and 4b by utilizing the difference in the temperature at which they condense (liquefy), respectively. It is also possible by doing. However, in this case, when the separated gas component is used in a high temperature state on the downstream side of the reactors 4a and 4b (for example, when it is used in the heat exchanger 102), it is necessary to heat it again. There is a waste of heat energy. On the other hand, according to the purifiers 14a and 14b, the gas component can be separated at a high temperature (for example, 200 to 500 ° C.), so that the temperature of the gas component after separation is unlikely to decrease. It can contribute to the reduction of thermal energy in the entire production of produced gas.
From the viewpoint of more reliably preventing the temperature of the gas component from dropping after separation by the refiners 14a and 14b, a heating device for heating the separation cylinder 141 (for example, an irradiation device for irradiating the microwave) is provided. You may do so.
　上述したように、各反応器４ａ、４ｂからは、比較的高温のガスが排出される。したがって、分離筒１４１は、耐熱性を備えることが好ましい。これにより、分離筒１４１の変質および劣化を防止することができる。
　かかる分離筒１４１は、金属、無機酸化物または金属有機構造体（Ｍｅｔａｌ　Ｏｒｇａｎｉｃ　Ｆｒａｍｅｗｏｒｋｓ：ＭＯＦ）で構成されていることが好ましい。この場合、分離筒１６１に優れた耐熱性を付与し易い。ここで、金属としては、例えば、チタン、アルミニウム、銅、ニッケル、クロム、コバルトまたはこれらを含む合金等が挙げられる。無機酸化物としては、例えば、シリカ、ゼオライト等が挙げられる。また、金属有機構造体としては、例えば、硝酸亜鉛水和物とテレフタル酸ジアニオンとの構造体、硝酸銅水和物とトリメシン酸トリアニオンとの構造体等が挙げられる。金属を用いる場合、分離筒１４１は、好ましくは、空孔率が８０％以上の多孔質材料で構成される。 As described above, relatively high temperature gas is discharged from each of the reactors 4a and 4b. Therefore, it is preferable that the separation cylinder 141 has heat resistance. Thereby, deterioration and deterioration of the separation cylinder 141 can be prevented.
It is preferable that the separation cylinder 141 is made of a metal, an inorganic oxide, or a metal-organic framework (MOF). In this case, it is easy to impart excellent heat resistance to the separation cylinder 161. Here, examples of the metal include titanium, aluminum, copper, nickel, chromium, cobalt, alloys containing these, and the like. Examples of the inorganic oxide include silica and zeolite. Examples of the metal-organic structure include a structure of zinc nitrate hydrate and terephthalate dianion, a structure of copper nitrate hydrate and trimesic acid trianion, and the like. When metal is used, the separation cylinder 141 is preferably made of a porous material having a porosity of 80% or more.
　分離筒１４１は、隣接する空孔同士が連通する連続空孔（筒壁を貫通する細孔）を備える多孔質体で構成されていることが好ましい。かかる構成の分離筒１４１であれば、水または一酸化炭素の透過率を高めて、水と水素との分離および／または一酸化炭素と二酸化炭素との分離をより円滑かつ確実に行うことができる。
　分離筒１４１の空孔率は、特に限定されないが、５～９５％であることが好ましく、１０～９０％であることがより好ましく、２０～６０％であることがさらに好ましい。これにより、分離筒１４１の機械的強度が極端に低下するのを防止しつつ、水または一酸化炭素の透過率を十分に高く維持することができる。
　なお、分離筒１４１の形状は、特に限定されず、円筒状、四角形、六角形のような角筒状等が挙げられる。 The separation cylinder 141 is preferably composed of a porous body having continuous pores (pores penetrating the cylinder wall) in which adjacent pores communicate with each other. With the separation cylinder 141 having such a configuration, the transmittance of water or carbon monoxide can be increased, and the separation of water and hydrogen and / or the separation of carbon monoxide and carbon dioxide can be performed more smoothly and reliably. ..
The porosity of the separation cylinder 141 is not particularly limited, but is preferably 5 to 95%, more preferably 10 to 90%, and even more preferably 20 to 60%. This makes it possible to maintain a sufficiently high transmittance of water or carbon monoxide while preventing the mechanical strength of the separation cylinder 141 from being extremely lowered.
The shape of the separation cylinder 141 is not particularly limited, and examples thereof include a cylindrical shape, a quadrangular shape, and a square cylinder shape such as a hexagon.
　ガス合流部Ｊ４において合流した後のガスの取扱性を向上させ（引火を未然に防止し）、生成ガスの製造効率を高く維持する観点からは、未反応の水素を除去することが有効である。
　すなわち、図８に示すように、反応器４ａ、４ｂを通過した水素（Ｈ２）および水（Ｈ２Ｏ）から、分離筒１４１を介して水をハウジング１４２内の空間１４３に移動させるように構成するのが好ましい。
　この場合、分離筒１４１の平均空孔径は、６００ｐｍ以下であるのが好ましく、４００～５００ｐｍであるのがより好ましい。これにより、水と水素との分離効率をより向上させることができる。
　なお、ハウジング１４２内の空間１４３は、減圧してもよいし、キャリアガス（スウィープガス）を通過させるようにしてもよい。キャリアガスとしては、例えば、ヘリウム、アルゴンのような不活性ガス等が挙げられる。 From the viewpoint of improving the handleability of the gas after merging in the gas merging portion J4 (preventing ignition) and maintaining high production efficiency of the produced gas, it is effective to remove unreacted hydrogen. ..
That is, as shown in FIG. 8, hydrogen (H 2 ) and water (H 2 O) that have passed through the reactors 4a and 4b are moved to the space 143 in the housing 142 via the separation cylinder 141. It is preferable to configure it.
In this case, the average pore diameter of the separation cylinder 141 is preferably 600 pm or less, and more preferably 400 to 500 pm. This makes it possible to further improve the separation efficiency of water and hydrogen.
The space 143 in the housing 142 may be depressurized or may be allowed to pass a carrier gas (sweep gas). Examples of the carrier gas include an inert gas such as helium and argon.
　また、分離筒１４１は、親水性を有することが好ましい。分離筒１４１が親水性を有すれば、水の分離筒１４１に対する親和性が高まり、水が分離筒１４１をより円滑に透過し易くなる。
　分離筒１４１に親水性を付与する方法としては、無機酸化物中の金属元素の比率を変更（例えば、Ａｌ／Ｓｉ比を高める等）して分離筒１４１の極性を向上させる方法、分離筒１４１を親水性ポリマーで被覆する方法、分離筒１４１を親水性基（極性基）を有するカップリング剤で処理する方法、分離筒１４１に対してプラズマ処理、コロナ放電処理等を行う方法等が挙げられる。
　さらに、分離筒１４１の表面電位を調整することにより、水に対する親和性を制御するようにしてもよい。 Further, the separation cylinder 141 is preferably hydrophilic. If the separation cylinder 141 has hydrophilicity, the affinity of water with respect to the separation cylinder 141 is enhanced, and it becomes easier for water to permeate the separation cylinder 141 more smoothly.
As a method of imparting hydrophilicity to the separation cylinder 141, a method of changing the ratio of metal elements in the inorganic oxide (for example, increasing the Al / Si ratio) to improve the polarity of the separation cylinder 141, the separation cylinder 141. A method of coating the separation cylinder 141 with a hydrophilic polymer, a method of treating the separation cylinder 141 with a coupling agent having a hydrophilic group (polar group), a method of subjecting the separation cylinder 141 to plasma treatment, corona discharge treatment, etc. ..
Further, the affinity for water may be controlled by adjusting the surface potential of the separation cylinder 141.
　一方、分離筒１４１において、一酸化炭素と二酸化炭素との分離を優先させて行う場合、水と水素との分離および一酸化炭素と二酸化炭素との分離の双方を同時に行う場合には、分離筒１４１の構成材料、空孔率、平均空孔径、親水性または疎水性の程度、表面電位等を適宜組み合わせて設定するようにすればよい。
　なお、精製器は、ガスラインＧＬ４の途中であって、ガス合流部Ｊ４とガス精製部９との間に設けるようにしてもよい。
　また、精製器１４ａ、１４ｂを設ける場合、上記ガス精製部９を省略するようにしてもよい。 On the other hand, in the separation cylinder 141, when the separation of carbon monoxide and carbon dioxide is prioritized, and when both the separation of water and hydrogen and the separation of carbon monoxide and carbon dioxide are performed at the same time, the separation cylinder is used. The constituent materials of 141, the pore ratio, the average pore diameter, the degree of hydrophilicity or hydrophobicity, the surface potential, and the like may be appropriately combined and set.
The refiner may be provided in the middle of the gas line GL4 between the gas confluence unit J4 and the gas purification unit 9.
Further, when the refiners 14a and 14b are provided, the gas purification unit 9 may be omitted.
　以上、本発明のガス製造装置、ガス製造システムおよびガス製造方法について説明したが、本発明は、これらに限定されるものではない。
　例えば、本発明のガス製造装置およびガス製造システムは、それぞれ上記実施形態に対して、他の任意の追加の構成を有していてもよく、同様の機能を発揮する任意の構成と置換されていてよく、一部の構成が省略されていてもよい。
　また、本発明のガス製造方法は、上記実施形態に対して、任意の目的の工程が追加されていてもよい。 Although the gas production apparatus, the gas production system, and the gas production method of the present invention have been described above, the present invention is not limited thereto.
For example, the gas production apparatus and the gas production system of the present invention may each have any other additional configuration with respect to the above embodiment, and are replaced with any configuration exhibiting the same function. However, some configurations may be omitted.
Further, in the gas production method of the present invention, any desired step may be added to the above embodiment.
　また、上記実施形態では、還元ガスとして水素を含むガスを代表に説明したが、還元ガスには、還元物質として、水素に代えてまたは水素とともに、炭化水素（例えば、メタン、エタン、アセチレン等）およびアンモニアから選択される少なくとも１種を含むガスを使用することもできる。
　また、上記実施形態では、反応器に供給する前の排ガス（原料ガス）、還元ガスまたは加熱用の媒体と、混合ガスとの間で熱交換する構成の熱交換器について説明したが、各反応器から排出され、混合ガスとされる前のガスと熱交換する構成の熱交換器を採用するようにしてもよい。 Further, in the above embodiment, a gas containing hydrogen as a reducing gas has been described as a representative, but the reducing gas includes a hydrocarbon (for example, methane, ethane, acetylene, etc.) as a reducing substance instead of hydrogen or together with hydrogen. And a gas containing at least one selected from ammonia can also be used.
Further, in the above embodiment, the heat exchanger having the configuration of exchanging heat between the exhaust gas (raw material gas), the reducing gas or the medium for heating before being supplied to the reactor and the mixed gas has been described, but each reaction has been described. A heat exchanger having a configuration that exchanges heat with the gas discharged from the vessel and before being made into a mixed gas may be adopted.
　１００…ガス製造システム
　１…ガス製造装置
　２…接続部
　３…還元ガス供給部
　４…反応部
　　４ａ、４ｂ…反応器
　　　４１…管体、４２…ハウジング、４３…空間、４４…隔壁部、４Ｒ…還元剤
　５…濃度調整部
　６…圧縮部
　７…微成分除去部
　８…ガス切換部
　９…ガス精製部
　１０…排ガス加熱部
　　１０１…電熱器、１０２…熱交換器
　１１…還元ガス加熱部
　１２…還元剤加熱部
　　１２１…移送装置、１２２…加熱装置、１２３…第１熱交換器、１２４…電熱器、
　　１２５…第２熱交換器
　１３…冷却部
　　１３１…冷却装置、１３２…容器
　１４ａ、１４ｂ…精製器
　　１４１…分離筒、１４２…ハウジング、１４３…空間
　２０…炉
　　２１…煙突、２２…分岐部、２３…ガスライン
　３０…タンク
　４０…生成ガス排出部
　ＧＬ１…ガスライン
　ＧＬ２…ガスライン
　ＧＬ３ａ、ＧＬ３ｂ…ガスライン
　ＧＬ４…ガスライン
　　ＧＬ４ａ、ＧＬ４ｂ…分岐ガスライン、Ｊ４…ガス合流部
　ＧＬ１４ａ、ＧＬ１４ｂ…ガスライン
　Ｌ１…離間距離
　Ｌ２…離間距離 100 ... Gas production system 1 ... Gas production equipment 2 ... Connection part 3 ... Reducing gas supply part 4 ... Reaction part 4a, 4b ... Reactor 41 ... Tube, 42 ... Housing, 43 ... Space, 44 ... Partition part, 4R ... Reducing agent 5 ... Concentration adjusting part 6 ... Compressing part 7 ... Fine component removing part 8 ... Gas switching part 9 ... Gas refining part 10 ... Exhaust gas heating part 101 ... Electric heater, 102 ... Heat exchanger 11 ... Reduced gas heating part 12 ... Reducing agent heating unit 121 ... Transfer device, 122 ... Heating device, 123 ... First heat exchanger, 124 ... Electric heater,
125 ... Second heat exchanger 13 ... Cooling unit 131 ... Cooling device, 132 ... Container 14a, 14b ... Purifier 141 ... Separation cylinder, 142 ... Housing, 143 ... Space 20 ... Furnace 21 ... Chimney, 22 ... Branching part, 23 ... Gas line 30 ... Tank 40 ... Generated gas discharge part GL1 ... Gas line GL2 ... Gas line GL3a, GL3b ... Gas line GL4 ... Gas line GL4a, GL4b ... Branch gas line, J4 ... Gas confluence part GL14a, GL14b ... Gas line L1 … Separation distance L2… Separation distance

Claims (8)

  1. 　二酸化炭素を含む原料ガスと、前記二酸化炭素を還元する金属酸化物を含む還元剤とを接触させて、一酸化炭素を含む生成ガスを製造するガス製造装置であって、
    　前記原料ガスを供給する原料ガス供給部と、
    　前記二酸化炭素との接触により酸化された前記還元剤を還元する還元物質を含む還元ガスを供給する還元ガス供給部と、
    　前記原料ガス供給部および前記還元ガス供給部にそれぞれ接続された複数の反応器と、前記反応器内に配置された前記還元剤とを備え、各前記反応器に供給する前記原料ガスと前記還元ガスとを切換可能な反応部とを有し、
    　前記反応器を通過した後のガス同士を合流させて、混合ガスを生成するガス合流部とを有し、
    　前記反応器へ所定の量の前記原料ガスを供給したとき、または、前記二酸化炭素の前記一酸化炭素への変換効率が所定の値を下回ったとき、各前記反応器に供給する前記原料ガスと前記還元ガスとを切り換えるように構成したことを特徴とするガス製造装置。     A gas production apparatus that produces a produced gas containing carbon monoxide by contacting a raw material gas containing carbon dioxide with a reducing agent containing the metal oxide that reduces carbon dioxide.
    The raw material gas supply unit that supplies the raw material gas and
    A reducing gas supply unit that supplies a reducing gas containing a reducing substance that reduces the reducing agent oxidized by contact with carbon dioxide, and a reducing gas supply unit.
    A plurality of reactors connected to the raw material gas supply unit and the reducing gas supply unit, and the reducing agent arranged in the reactor are provided, and the raw material gas and the reduction are supplied to each of the reactors. It has a reaction unit that can switch between gas and gas.
    It has a gas merging portion that merges the gases after passing through the reactor to generate a mixed gas.
    When a predetermined amount of the raw material gas is supplied to the reactor, or when the efficiency of converting carbon dioxide to carbon monoxide falls below a predetermined value, the raw material gas supplied to each of the reactors is used. A gas production apparatus characterized in that it is configured to switch between the reduced gas and the reduced gas.
  2. 　前記反応器への前記原料ガスの供給量をＰ［ｍＬ／分］とし、前記反応器への前記還元ガスの供給量をＱ［ｍＬ／分］としたとき、Ｐ／Ｑが０．９～２なる関係を満足する請求項１に記載のガス製造装置。 When the supply amount of the raw material gas to the reactor is P [mL / min] and the supply amount of the reducing gas to the reactor is Q [mL / min], the P / Q is 0.9 to The gas production apparatus according to claim 1, which satisfies the relationship of 2.
  3. 　前記所定の量は、前記還元剤に占める質量の割合が最も多い金属元素１モル当たり、前記二酸化炭素が０．０１～３モルの量である請求項１または２に記載のガス製造装置。 The gas production apparatus according to claim 1 or 2, wherein the predetermined amount is 0.01 to 3 mol of carbon dioxide per 1 mol of the metal element having the largest mass ratio in the reducing agent.
  4. 　前記所定の値は、５０～１００％である請求項１～３のいずれか１項に記載のガス製造装置。 The gas production apparatus according to any one of claims 1 to 3, wherein the predetermined value is 50 to 100%.
  5. 　さらに、前記混合ガスと、前記反応器に供給する前の前記原料ガスとの間で熱交換する熱交換器を有する請求項１～４のいずれか１項に記載のガス製造装置。 The gas production apparatus according to any one of claims 1 to 4, further comprising a heat exchanger that exchanges heat between the mixed gas and the raw material gas before being supplied to the reactor.
  6. 　前記金属酸化物は、第３族～第１２族に属する金属元素から選択される少なくとも１種を含有する請求項１～５のいずれか１項に記載のガス製造装置。 The gas production apparatus according to any one of claims 1 to 5, wherein the metal oxide contains at least one selected from metal elements belonging to Group 3 to Group 12.
  7. 　二酸化炭素を含む原料ガスを生成する原料ガス生成部と、
    　請求項１～６のいずれか１項に記載のガス製造装置とを備え、
    　前記ガス製造装置が、前記原料ガス供給部を介して前記原料ガス生成部に接続されていることを特徴とするガス製造システム。     A raw material gas generator that generates raw material gas containing carbon dioxide,
    The gas production apparatus according to any one of claims 1 to 6 is provided.
    A gas production system characterized in that the gas production apparatus is connected to the raw material gas generation unit via the raw material gas supply unit.
  8. 　二酸化炭素を含む原料ガスと、前記二酸化炭素を還元する金属酸化物を含む還元剤とを接触させて、一酸化炭素を含む生成ガスを製造するガス製造方法であって、
    　前記還元剤を内部に配置した複数の反応器と、前記原料ガスと、前記二酸化炭素との接触により酸化された前記還元剤を還元する還元物質を含む還元ガスとを準備し、
    　前記原料ガスと前記還元ガスとを供給する前記反応器を切り換えることにより、各前記反応器内において前記還元剤に前記原料ガスと前記還元ガスとを交互に接触させて、前記二酸化炭素を前記一酸化炭素に変換した後、前記酸化された還元剤を還元し、
    　前記反応器を通過した後のガス同士を合流させて、混合ガスを生成し、
    　前記混合ガスをそのまま、または、前記混合ガスから前記一酸化炭素を精製することにより、前記生成ガスとして回収するのに際して、
    　前記反応器へ所定の量の前記原料ガスを供給したとき、または、前記二酸化炭素の前記一酸化炭素への変換効率が所定の値を下回ったとき、各前記反応器に供給する前記原料ガスと前記還元ガスとを切り換えることを特徴とするガス製造方法。     A gas production method for producing a produced gas containing carbon monoxide by contacting a raw material gas containing carbon dioxide with a reducing agent containing the metal oxide that reduces carbon dioxide.
    A plurality of reactors in which the reducing agent is arranged, a reducing gas containing the raw material gas and a reducing substance that reduces the reducing agent oxidized by contact with the carbon dioxide are prepared.
    By switching the reactor that supplies the raw material gas and the reducing gas, the raw material gas and the reducing gas are alternately brought into contact with the reducing agent in each of the reactors, and the carbon dioxide is brought into the one. After converting to carbon oxide, the oxidized reducing agent is reduced to reduce it.
    The gases after passing through the reactor are merged to generate a mixed gas.
    When recovering the mixed gas as it is or by purifying the carbon monoxide from the mixed gas as the produced gas.
    When a predetermined amount of the raw material gas is supplied to the reactor, or when the efficiency of converting carbon dioxide to carbon monoxide falls below a predetermined value, the raw material gas supplied to each of the reactors is used. A gas production method characterized by switching from the reduced gas.
PCT/JP2020/029820 2020-08-04 2020-08-04 Gas production apparatus, gas production system, and gas production method WO2022029884A1 (en)

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JP2015016467A (en) * 2013-06-21 2015-01-29 アルストム テクノロジー リミテッドＡＬＳＴＯＭ Ｔｅｃｈｎｏｌｏｇｙ Ｌｔｄ Chemical looping integration with carbon dioxide gas purification unit
JP5858926B2 (en) 2010-10-26 2016-02-10 三井金属鉱業株式会社 Carbon monoxide production method and production apparatus
WO2019163968A1 (en) * 2018-02-22 2019-08-29 積水化学工業株式会社 Carbon dioxide reduction system and carbon dioxide reduction method
KR20200055939A (en) * 2018-11-14 2020-05-22 전북대학교산학협력단 Manufacturing method for carbon monoxide by chemical looping combustion

Patent Citations (4)

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JP5858926B2 (en) 2010-10-26 2016-02-10 三井金属鉱業株式会社 Carbon monoxide production method and production apparatus
JP2015016467A (en) * 2013-06-21 2015-01-29 アルストム テクノロジー リミテッドＡＬＳＴＯＭ Ｔｅｃｈｎｏｌｏｇｙ Ｌｔｄ Chemical looping integration with carbon dioxide gas purification unit
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KR20200055939A (en) * 2018-11-14 2020-05-22 전북대학교산학협력단 Manufacturing method for carbon monoxide by chemical looping combustion

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